Yulia Chapurina

Thierry Roisnel

Jean-François Carpentier
email: jean-francois.carpentier@univ-rennes1.fr

Evgeny Kirillov
email: evgueni.kirillov@univ-rennes1.fr

Zinc, Aluminum and Group 3 Metal Complexes of Sterically Demanding Naphthoxy-Pyridine Ligands: Synthesis, Structure, and Use in ROP of racemic Lactide and -Butyrolactone

Zinc, aluminum and group 3 metal complexes of sterically demanding naphthoxy-pyridine ligands: Synthesis, structure, and use in ROP of racemic lactide and β-butyrolactone

For the Table of content entry

Zinc, aluminum and group 3 metal complexes supported by tridentate naphthoxy-pyridine ligands were prepared and used as initiators/catalysts for the ring-opening polymerization of racemic-lactide and racemic--butyrolactone, affording heterotactic-enriched PLAs and atactic PHBs, respectively.

Introduction

Stereocontrolled ring-opening polymerization (ROP) of racemic cyclic esters (e.g., lactide (rac-LA) and β-butyrolactone (rac-BBL)), mediated by discrete organometallic precursors, has been the subject of numerous studies in the last years. 1 Polymerization of these renewable monomers under appropriate conditions can lead to polymers exhibiting a wide range of microstructures (iso/hetero(syndio)/atactic, and also stereoblock and gradient), which may confer, in each specific case, high crystallinity, improved elastomeric properties and controlled biodegradability. The ligand nature (geometry) plays a pivotal role in the polymerization stereocontrol, even if stereoselection during coordination/insertion of the monomer onto a metal center occurs via a chain-end control (CEM) rather than an enantiomorphic site control mechanism (SCM), which is the more "natural" process for chirality transfer onto a growing polymeric chain. 1,2 In our ongoing survey of new ancillaries for engineering of potent catalysts/initiators for stereocontrolled ROP of cyclic esters, we have designed a bis(naphthoxy)pyridine ligand platform (Scheme 1). 3,4 The non-coplanar orientation of the bridging pyridine and adjacent naphthoxy groups within the latter system, upon stereoselective coordination with group 4 metals (Ti, Zr and Hf), can give rise to two distinct geometries, namely, C s -symmetric (mesolike) and C 2 -symmetric (rac-like) isomers. 5 This interconversion between two geometries is anticipated to exert some special influence on the stereocontrollablity of the metal complexes towards the polymerizations of cyclic esters such as rac-LA and rac-BBL, leading to polyesters with different tacticities (e.g., atactic or hetero/syndiotactic). Also, if such interconversion would occur on the timescale of polymerization propagation ("oscillating" behavior), it could lead to stereoblock architectures (i.e., macromolecules enchaining segments of different tacticities). In fact, reversible interconversion between such C s -and C 2symmetric isomers of group 4 metal complexes has been demonstrated to take place in toluene solution with a moderate activation barrier (∆G ≠ 298 = 13.8-15.6 kcal•mol -1 ). Yet, in our previous attempts intended to extend this coordination chemistry to groups 3 (Sc, Y and La) and 13 (Al) metals, for each compound, solely the isomer exhibiting the C s -symmetric coordination of the ligand has been observed and isolated. 5 For all of these different complexes, interconversion between the C s -and a putative C 2 -symmetric isomers was not observed in solution using VT NMR spectroscopic studies. The latter behavior may stem either from a much higher interconversion barrier (kinetic control), intrinsic to such bis(naphthoxy)pyridine complexes of groups 3 and 13 metals, or from basic instability of the associated C 2 -isomer (thermodynamic control). When used as initiators/precatalysts in ROP of rac-LA and rac-BBL, these group 3 metal bis(naphthoxy)pyridine complexes were found to be moderately heteroselective and syndioselective, respectively, while the aluminum complexes appeared to be non-stereoselective. 5 Scheme 1. Ph 3 Si-substituted bis(naphthoxy)pyridine-based polymerization systems.

Thus, we decided to set up more flexible ligand platforms that combine the conformationally stable naphthoxy-pyridine scaffold and pending heteroatom-containing donating groups. We surmised that the implementation of these ligands would provide a less sterically rigid binding with metal center 6 and would allow preparation of complexes featuring relatively easy dynamic interconversion between isomers of different geometries.

In this contribution, two main categories of asymmetrically substituted pyridinenaphthol proligands were considered (Scheme 2): (i) proligands a----d bearing O-based pendant donating groups, which would result in monoanionic {ONO} -ligand platforms, and (ii) proligands incorporating N-based pendant donating groups for the synthesis of complexes with both monoanionic {ONN} -(e) and dianionic {ONN} 2-(f) ligand platforms. The synthesis of the corresponding complexes of zinc, aluminum and group 3 metals (Sc, Y and La) was investigated, and the obtained compounds were studied as initiators in the ROP of rac-LA and rac-BBL.

Scheme 2. Tridentate pyridine-linked naphthol-based proligands a-f used in this study.

Results and Discussion

Synthesis of Proligands. Asymmetric pyridine-linked proligands a and b were prepared starting from the diproteo bis(naphthol)pyridine proligand previously described by our group (Scheme 3). 5a The two-step procedure involves deprotonation of the latter precursor with PhCH 2 K in THF followed by methylation or benzylation reaction with MeI or BnBr/Bu 4 NI to afford a and b, respectively. Analytically pure proligands were obtained after column chromatography in 49% and 46% yields, respectively. Section) and the corresponding boronic acid, followed by deprotection (Scheme 4). Both compounds were obtained in 66% and 94% yields, respectively, after recrystallization. S1 andS2). In a similar manner, dimethyl-aluminum complex 3c was prepared by treatment of the parent proligand with a small excess of AlMe 3 in toluene at room temperature and isolated as a red crystalline solid in 88% yield (Scheme 6). Due to difficulties encountered for Zn and Ln (vide infra) chemistries, neither a nor b were tested with Al.

Synthesis of Zinc

The complexes were characterized by NMR spectroscopy in solution and elemental analysis and X-ray crystallography in the solid state (vide infra). The 1 H and 13 C{ 1 H} NMR spectra of 1a, 1c, 1d, 2c, 2d and 3c confirm the nature of the compounds. In particular, the We also investigated the coordination of an {ONO} ligand on group 3 metals through aminolysis of Ln[N(SiHMe 2 ) 2 ] 3 THF (Ln = Y, La) with an equimolar amount of a. The reactions were monitored by 1 H NMR spectroscopy in toluene-d 8 at 25 °C. Under these conditions, complete consumption of the proligand, accompanied with concomitant release of 1 equiv of HN(SiHMe 2 ) 2 , was observed within 18 h for both yttrium and lanthanum.

Unfortunately, the 1 H NMR spectra of both products appeared to remain very broad over the large temperature range -50 to +80 °C, and these NMR data were not conclusive as to the nature of the product(s) formed. Also, all attempts to crystallize these materials failed. Due to these difficulties, the coordination chemistry of other {ONO} ligands with group 3 metals was not further investigated.

Ligands of ONN-type.

Analogous reactivity studies were performed for the {ONN}-type proligand e (Scheme 7). Reaction of e with 1 equiv of Zn[N(SiMe 3 ) 2 ] 2 gave the desired complex 2e with high yield. On the other hand, using a similar protocol as that employed for the synthesis of 3c, the reaction of e with 1 equiv of AlMe 3 afforded after a standard workup, instead of the desired 3e, the monomethyl-aluminum complex 3e'

containing a new dianionic {ONN} 2-ligand. This result is in line with previous observations made on the coordination of imino-based ligands on AlMe 3 , which typically resulted in nucleophilic addition of a methyl group on the C=N bond. 9

Reaction of e with 1 equiv of Y[N(SiHMe 2 ) 2 ] 3 THF successfully yielded the corresponding THF-free diamido compound 4e (Scheme 7).

Scheme 7. Synthesis of {ONN} -and {ONN} 2-complexes of Zn (2e), Al (3e') and Y (4e).

Complexes 2e, 3e' and 4e were characterized by 1 H, 13 C{ 1 H} and [START_REF]1 J Si-H = 165, 2Si)[END_REF] Si (for 4e) NMR spectroscopy in solution, and elemental analysis and X-ray diffraction study (for 2e) in the solid state. The fluxional dynamic behavior observed for 2e and 4e in benzene solution (Fig. S32, S38 and S40) may arise from hindered rotation associated to the bulky diisopropylphenyl and amido groups. All three complexes featured asymmetric structures in solution, as revealed by 1 H and 13 C{ 1 H} NMR spectroscopy. For instance, the iPr groups of the diisopropylphenyl groups gave rise to two sets of signals in the corresponding NMR spectra.

In 4e, the two N(SiHMe 2 ) 2 groups were also found non-equivalent and appeared as two sets of signals in the corresponding 1 H, 13 C and [START_REF]1 J Si-H = 165, 2Si)[END_REF] Si NMR spectra (Figures S38, S39 and S42, respectively); those signals do not coalesce, even upon heating at 60 °C.

The amine elimination reactions between f and 1 equiv of Ln[N(SiHMe 2 ) 2 ] 3 THF (Ln = Sc, Y and La) were investigated (Scheme 8). The reactions took place at 50 °C overnight with complete consumption of the proligand and concomitant release of 2 equiv of HN(SiHMe 2 ) 2 to afford 5f (Y) and 6f (La). For the Sc analogue 4f, an extended reaction time (one week) was required for completion of the reaction. This reactivity trend is in agreement with the larger ionic character of Y and La (Y +3 (CN = 6): 0.90 Å, La +3 (CN = 6): 1.03 Å) as compared to that of Sc (Sc +3 (CN = 6): 0.75 Å). 10 After a standard workup, the monoamido complexes 4----5f of the dianionic {ONN}-type ligand were isolated in good yields (67-83%).

Scheme 8. Synthesis of {ONN} 2-complexes of Sc (4f), Y (5f) and La (6f).

These compounds are readily soluble in aromatic hydrocarbons (benzene, toluene) and in THF. The structures of these complexes were established on the basis of 1 H, 13 C{ 1 H},

Studies on Ring-Opening Polymerization of rac-Lactide (rac-LA) and rac-

Butyrolactone (rac-BBL).

The new zinc, aluminum and group 3 metals complexes have potentially active nucleophilic groups (i.e., alkyl and amido) and their performances as initiators of the ROP of racemic lactide and β-butyrolactone were assessed. Representative results are summarized in Tables 1 and2.

(insert Table 1 here) Zinc-based Initiators. Not surprisingly in light of the poor nucleophilicity of the ethyl group, zinc ethyl complexes 1a, 1c and 1d proved to be quite poor initiators in the ROP of rac-LA. The polymerization did not take place at room temperature and substantial heating (60-100 °C) was required to achieve high conversions. Complex 1a containing the Ph 3 Si-disubstituted bis(naphthoxy) ligand was not active even under these conditions (Table 1, entries 1 and 2). When combined with isopropanol (5 equiv), 1a appeared to be active at 100 °C, slowly converting 100 and 1,000 equiv of lactide (entries 3 and 4, respectively). The atactic PLAs formed under those conditions had unimodal, although broadened molecular distributions with the experimental number-average molecular weights being close to the calculated ones (based on the converted monomer-to-alcohol ratio).

Complexes with the less bulky ligands 1c and 1d exhibited higher activity than 1a

and enabled the conversion of 100 equiv of rac-lactide within a few minutes at 80 °C in toluene or at 60°C in THF solution, even without addition of isopropanol (entries 6, 7 and 5, respectively). The resulting slightly heterotactic-enriched PLAs (P r = 0.65-0.75) have relatively broad molecular distributions (Ð M = 1.5-2.1).

As expected, the more nucleophilic amide-zinc complexes 2c, 2d and 2e proved to be active at room temperature, enabling the conversion of 100-2,000 equiv of rac-LA within relatively short periods of time (entries 8-12, 15-17). The PLAs obtained with 2c and 2d under these conditions had also unimodal, yet rather broad molecular weight distributions (Ð M = 1.3-2.0), which argues for their unoptimal initiation efficiency and/or propensity to promote side-reactions such as transesterification. Remarkably, 2e even without iPrOH (entries 16 and 17) afforded PLAs with rather narrow polydispersities (Ð M = 1.11) and good agreement between the experimental and calculated molecular weights. The presence of isopropanol turned out to be detrimental for the activities of these systems. For instance, the combinations of 2c or 2e with iPrOH (one equiv) were completely inactive at room temperature (entries 13, 18 and 19). Actually, an NMR monitoring of the reaction of 2c with one equiv of isopropanol in toluene-d 8 at room temperature indicated decomposition of the complex with release of protio c. Homo-decoupled 1 H NMR spectroscopy showed that the PLAs obtained with systems 2c, 2d and 2e all had a slightly heterotactic-enriched microstructures (P r = 0.65-0.76).

The performance of 2c and 2e, the most active complexes towards rac-LA, were next assessed in the ROP of rac-BBL. Polymerization occurred only upon heating at 60-80 °C and complete conversions were reached after longer time periods (Table 2, entries 2 and 3).

Despite the absence of co-initiator / chain-transfer agent (iPrOH), the initiation with these systems appeared remarkably efficient and PHBs featuring narrow molecular weight distributions were isolated (Ð M = 1.07-1.23). Yet, the experimental number average molecular weights were not systematically close to the calculated ones. Also, polymerizations with 2c and 2e were found to be essentially nonstereoselective.

(insert Table 2 Within the f series, the activity of complexes clearly follows the order of ionic radii of metals La(6f) > Y(5f) > Sc(4f). Thus, for scandium complex 4f, a substantial heating was required to achieve a good conversion (entry 29). Such trend was already observed for a similar series of group 3 metal amino-alkoxy-bis(phenolate) complexes and was explained on account of a more sterically hindered metal center. 17 These lanthanide systems provided relatively broad molecular weight distributions (Ð M = 1.4-2.0), which do not improve much if isopropanol is used as chain-transfer agent (compare entries 30/33 and 34/35). Homodecoupled 1 H NMR spectroscopy showed that the PLAs formed with these systems have heterotactic-enriched microstructures with the probability of racemic linkage ranging from 0.78-0.80 for 4e to 0.57-0.69 for 4----6f.

In line with previous reports, 5b,17 the activities of complexes 4e and 4----6f in the ROP of rac-BBL were found inferior to those of rac-LA (Table 2, entries 10-14). For instance, polymerization reactions with 5f and 6f required longer periods of time, while with 4f they did not take place at all even at 60 °C. For the most active 4e, the TOF was up to 900 mol(BBL)•mol(Y) -1 •h -1 at 25 °C. The resulting PHBs had molecular weights distributions that were unimodal, although somewhat large (Ð M = 1.5-1.9). None of these complexes proved to be stereoselective, giving mostly atactic PHB polymers (P r = 0.42-0.66).

Conclusions

Several new series of bulky Ph 3 Si-substituted tridentate naphthol-pyridine proligands have been conveniently prepared and straightforwardly installed onto Zn, Al and group 3 metals (Sc, Y and La) as alkyl and amido complexes. These monomeric and monometallic complexes all adopt C 1 -symmetry both in the solid state and in solution (benzene, toluene or THF).

Studies in the ROP of rac-LA and rac-BBL indicated that some of these systems exhibit significant activity, good molecular weight control and narrow molecular weight distributions. On the other hand, modest degrees of stereocontrol were achieved with these systems. The performances of the complexes obtained in this study compare well with that of their corresponding imino-phenoxide and related analogues. The combined organic layers were dried over magnesium sulfate and evaporated to yield a yellowish solid. The product was purified by passing through a short silica column using CH 2 Cl 2 as eluent, to afford the product as an off-white solid (5.45 g, 85%). and dried toluene (ca. 10 mL) was transferred in. ZnEt 2 (0.12 mL of a 1.0 M solution in toluene, 0.12 mmol) was added to the reaction mixture at -78 °C. The reaction mixture was gently warmed to room temperature and stirred 12 h. The solution was filtered, evaporated, and the residue was washed with pentane and dried under vacuum to give 1a as a yellow microcrystalline material (0.100 g, 90%). 1 Complex 1c. Using a procedure similar to that described above for 1a, compound 1c was obtained from c (0.100 g, 0.157 mmol) and ZnEt 2 (0.17 mL of a 1.0 M solution in toluene, 0.17 mmol) and isolated as a yellow microcrystalline material (0.111 g, 97%).

Scheme 3 .

 3 Scheme 3. Synthesis of proligands a and b.

Scheme 4 .Scheme 5 .

 45 Scheme 4. Synthesis of proligands c and d.

, Aluminum and Group 3 1 .

 31 Metal Complexes. The preparation of alkyl-and amido-zinc complexes supported by these bulky naphthoxy-based ligands was carried out by direct σ-bond metathesis of ZnEt 2 and Zn[N(SiMe 3 ) 2 ] 2 , respectively, with proligands a----d. Generally, the reactions took place in toluene at room temperature, concomitantly eliminating 1 equiv of ethane or HN(SiMe 3 ) 2 , respectively. Ligands of ONO-type. Within the series of complexes of {ONO} -ligands (Scheme 2, top), both the corresponding ethyl-zinc (1a, 1c and 1d) and amido-zinc (2c and 2d) compounds were isolated in high yields. The reaction of b with Zn[N(SiMe 3 ) 2 ] 2 appeared to be problematic, and mixtures of the desired complex 2b with the initial proligand were systematically obtained. The outcome of these tests did not change even upon heating at 80 °C over one week. The reasons for such reactivity remained unclear, and 1b was not isolated pure. The reaction of b with Et 2 Zn did not take place in benzene or toluene even upon reflux.

Scheme 6 .

 6 Scheme 6. Synthesis of {ONO} -complexes of Zn (1a----d, 2d and 2c) and Al (3c).

Figure 4 .

 4 Figure 4. Solid-state molecular structure of 2c (thermal ellipsoids drawn at 50% probability; all hydrogen atoms are omitted for clarity). Selected bond distances (Å) and angles (deg): Zn(1)-O(1), 1.9363(13); Zn(1)-O(2), 2.1454(13); Zn(1)-N(1), 2.0422(16); Zn(1)-N(2), 1.9015(16); N(1)-Zn(1)-N(2), 131.71(7); O(1)-Zn(1)-O(2), 97.65(5); Zn(1)-O(2)-C(1), 118.08(12); O(1)-Zn(1)-N(1), 90.57(6); O(2)-Zn(1)-N(1), 84.98(6); O(1)-Zn(1)-N(2), 127.68(7), O(2)-Zn(1)-N(2), 112.96(6).

Figure 5 .

 5 Figure 5. Solid-state molecular structure of 2e (thermal ellipsoids drawn at 50% probability; all hydrogen atoms are omitted for clarity). Selected bond distances (Å) and angles (deg): Zn(1)-O(1), 1.979(3); Zn(1)-N(1), 2.037(3); Zn(1)-N(2), 1.902(3); Zn(1)-N(3), 2.162(3); N(3)-C(1), 1.276(5); N(1)-Zn(1)-N(2), 130.35(13); O(1)-Zn(1)-N(3), 119.03(11); Zn(1)-

Figure 6 .

 6 Figure 6. Solid-state molecular structure of 3c . C 4 H 8 O (thermal ellipsoids drawn at 50% probability; all solvent molecules and hydrogen atoms are omitted for clarity). Selected bond distances (Å) and angles (deg): Al(1)-O(1), 1.781(2); Al(1)-N(1), 2.023(2); Al(1)-C(2_1), 1.968(4); Al(1)-C(2_2), 1.943(3); O(1)-Al(1)-N(1), 92.13(9); O(1)-Al(1)-C(2_1), 111.78(12); O(1)-Al(1)-C(2_2), 106.12(13), N(1)-Al(1)-C(2_1), 110.30(12); N(1)-Al(1)-C(2_2), 112.21(12).

Figure 7 .

 7 Figure 7. Solid-state molecular structure of 3e'' (thermal ellipsoids drawn at 50% probability; all hydrogen atoms are omitted for clarity). Selected bond distances (Å) and angles (deg): Al(1)-O(1), 1.7794(15); Al(1)-N(1), 1.9318(17); Al(1)-N(2), 1.817(2); N(2)-C(1), 1.473(3); Al(1)-O(3), 1.690(2); N(1)-Al(1)-N(2), 86.52(8); O(1)-Al(1)-N(1), 89.15(7); Al(1)-N(2)-C(1), 115.64(14); N(2)-C(1)-C(2), 112.6(2); O(1)-Al(1)-N(2), 124.66(8), Al(1)-O(3)-Al(2), 154.80(9).

SiMe 4

 4 and were determined by reference to the residual solvent peaks. Assignment of resonances for organometallic complexes was made from 2D 1 H-13 C HMQC and HMBC NMR experiments.[START_REF]1 J Si-H = 165, 2Si)[END_REF] Si chemical shifts were determined with respect to the external reference (Me 4 Si).Elemental analyses (C, H, N) were performed on recrystallized samples that were thoroughly dried under vacuum, using a Flash EA1112 CHNS Thermo Electron apparatus and are the average of two independent determinations.Size exclusion chromatography (SEC) analyses of PLAs andPHBs were performed in THF (1.0 mL.min -1 ) at 20 °C using a Polymer Laboratories PL-GPC 50 plus apparatus equipped with two ResiPore 300 × 7.5 mm columns, and RI and Dual angle LS (PL-LS 45/90) detectors. The number-average molecular masses (M n ) and polydispersity index (M w /M n ) of the polymers were calculated with reference to a universal calibration vs. polystyrene standards. Reported experimental SEC molar mass values (M n , SEC ) for PLA samples were corrected by a factor of 0.58 as previously established; 21 those of PHBs are uncorrected. Unless otherwise stated, the SEC traces of the polymers all exhibited a unimodal, and usually symmetrical, peak. To a solution of [3-(methoxymethoxy)-2-naphthyl)](triphenylsilane)3 (5.00 g, 11.19 mmol) in THF (100 mL) was added TMEDA (1.67 mL, 11.21 mmol) followed by addition of sec-BuLi (9.12 mL of a 1.3 M solution in hexane/cyclohexane, 11.86 mmol) at -78 °C. The reaction mixture was stirred at room temperature overnight. Then, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.65 mL, 17.90 mmol) was added via syringe at -78 °C. After 30 min at -78 °C, the flask was removed from the cooling bath and allowed to warm to room temperature while stirring; the reaction mixture was stirred at 70°C overnight. The reaction was quenched with saturated aqueous ammonium chloride and extracted with CH 2 Cl 2 (3 × 50 mL).

  Hence, the room-temperature 1 H NMR spectrum of 1a in toluene-d 8 (FigureS23) displayed a series of broadened signals due to fluxional dynamics arising from a hindered reorganization of the geometry (presumably, via reversible decoordination and rotation of the bulky MeO-naphthyl moiety and/or reciprocal reorganization of the adjacent naphthoxy and pyridine moieties). Upon lowering the temperature, all signals sharpened and a well-resolved NMR spectrum for this compound was recorded at -20 °C (FiguresS20-S22), consistent with the presence of a single C 1 -symmetric species. For other compounds in this series, this reorganization process appeared to be more

	-1.2 and 12.8 (1c), -2.4 and 12.3 (1d) ppm), Zn-N(SiMe 3 ) 2 (δ 5.4 (2c), 5.5 (2d) and 4.9 (2e)
	ppm) and Al-Me (δ -9.7 (3c) and -14.2 (3e) ppm) groups are in line with those reported in
	the literature for analogous Zn-ethyl, 7 Zn-amido 8 and Al-methyl 4,5b,c complexes. These NMR

13

C NMR chemical shifts (less sensitive than 1 H signals to anisotropic effects quite likely in those complexes having multiple aromatic rings) for the Zn-CH 2 CH 3 (δ -1.8 and 11.8 (1a), data also all testify of the asymmetric nature of these complexes in solution. Due to the substantial bulkiness of the ligand scaffolds, some of the complexes (1a and 1d) exhibited a moderate fluxional behavior. facile and the corresponding 1 H NMR spectra all displayed sharp resonances at room temperature (see the SI).

Solid-State Structures of Zinc and Aluminum Complexes. Single

	temperature range, as judged from the 1 H NMR data obtained for 5f (Figure S51). Also, no Å). This elongation can probably be a result of a significant steric Figure 2. Solid-state molecular structure of 1c (thermal ellipsoids drawn at 50% probability;
	interconversion between asymmetric species having different geometries was evidenced for hindrance in 2e. all hydrogen atoms are omitted for clarity). Selected bond distances (Å) and angles (deg):
	the latter species by variable-temperature 1 H NMR spectroscopy. 12 Zn(1)-O(1), 1.9386(18); Zn(1)-N(1), 2.133(2); Zn(1)-C(2), 1.977(3); Zn(1)-O(3), 2.138(2);
	crystals of zinc Zn(1)-C(2)-C(3), 119.6(2); O(1)-Zn(1)-O(3), 91.08(8); O(3)-Zn(1)-N(1), 89.60(8); O(1)-
	and aluminum complexes suitable for X-ray diffraction analysis were obtained from the Zn(1)-N(1), 91.23(8); C(2)-Zn(1)-N(1), 133.03(11).
	following mixtures: C 6 H 6 /heptane (1d . 1.5C 6 H 6 ,), THF/hexane (1c and 3c . C 4 H 8 O) and
	toluene/hexane (1a . 0.5C 7 H 8 , 2c and 2e). The crystallographic data of these complexes are
	summarized in Table S3 and important bond distances and angles are given in the
	corresponding Figures 1-6.
	In the solid state, all the complexes feature a monomeric structure with the metal
	center in a distorted tetrahedral geometry. The common feature observed in these molecular
	structures lies in the non-coplanarity of the naphthoxy and pyridine planes. The twist angles Figure 1. Solid-state molecular structure of 1a . 0.5C 7 H 8 (thermal ellipsoids drawn at 50%
	between these two fragments range from 42.04 to 55.8°, which falls within the range of values probability; all solvent molecules and hydrogen atoms are omitted for clarity). Selected bond
	(38.7-64.4°) observed for related bis(naphthoxy)pyridine complexes of group 3 and 4 distances (Å) and angles (deg): Zn(1)-O(1), 1.912(4); Zn(1)-O(2), 2.238(4); Zn(1)-N(1),
	metals. 3,5 2.103(2); Zn(1)-C(2), 1.956(3); Zn(1)-C(2)-C(3), 112.0(2); O(1)-Zn(1)-O(2), 97.2(2); Figure 3. Solid-state molecular structure of 1d . 1.5C 6 H 6 (thermal ellipsoids drawn at 50%
	In zinc complexes 1a, 1d, 2c and 2e, the metal center lies in a (distorted) tetrahedral Zn(1)-O(2)-C(1), 125.3(2); O(1)-Zn(1)-N(1), 90.3(7); O(2)-Zn(1)-N(1), 79.5(7); C(2)-probability; all solvent molecules and hydrogen atoms are omitted for clarity). Selected bond
	environment, coordinated by the tridentate ligands and the ethyl or bis(trimethylsilyl)amido Zn(1)-N(1), 116.55(11). distances (Å) and angles (deg): Zn(1)-O(1), 1.9390(18); Zn(1)-O(2), 2.265(2); Zn(1)-N(1),
	group. In 1c, the ligand is only κ 2 -coordinated by its O(naphthoxy) and N(pyridine) and the 2.065(2); Zn(1)-C(2), 1.960(3); Zn(1)-C(2)-C(3), 116.4(2); O(1)-Zn(1)-O(2), 95.52(8);
	metal center is also four-coordinated by an additional THF molecule (instead of the ligand Zn(1)-O(2)-C(1), 116.23(18); O(1)-Zn(1)-N(1), 88.65(8); O(2)-Zn(1)-N(1), 79.05(8);
	29 Si{ 1 H} and 29 Si NMR spectroscopy and elemental analysis. By analogy with group 3 metal methoxy, in contrast to 1d). The Zn-O(naphthoxy) (1.912(4)-1.979(3) Å), Zn-N(pyridine) C(2)-Zn(1)-N(1), 130.94(11).
	complexes of dianionic bis(naphthoxy)pyridine ligands, 5b the mono-THF adducts 4f-6f are (2.037(3)-2.133(2) Å), Zn-C(ethyl) (1.956(3)-1.977(3) Å) and Zn-N(amido)
	most probably mononuclear and five-coordinate in benzene or toluene solutions. The (1.9015(16)-1.902(3) Å) bond lengths are in the range of, or are close to those observed in
	chemical shifts of the SiH moiety (δ 4.70-4.84 ppm at room temperature in C 6 D 6 ) for 4f, 5f related compounds (2.021(2)-2.029(2), 13 1.962(2)-2.054(4), 7,8,14 1.958(3)-1.981(2) 7,14,15 and
	and 6f and the 1 J Si-H coupling constants (180, 165 and 163 Hz, respectively) were found in the 1.869(2)-1.920(4) Å, 8 respectively). Noteworthy, the Zn-N(imino) bond distance in 2e
	regular range of values, arguing against strong β-Si-H … Ln agostic interactions with the metal (2.162 (3) Å) is ca. 0.1 Å longer than that reported for related compounds (1.872(1)-1.977(4)
	centers in solution. 11 The structures of all complexes are asymmetric in solution over a broad

  = 1.17-1.37) and the good agreement between observed and theoretical molecular weights calculated on the assumption of the growth on one macromolecular chain per metal center. The homo-decoupled1 H NMR experiments conducted on the PLAs samples produced with these aluminum compounds indicated that all of them are atactic. On the other hand, complexes 3c and 3e' were found completely inactive towards rac-BBL (Table2, entries 7-9), which is not unsurprising for aluminum complexes.1

	Group 3 Metal-based Initiators. The group 3 diamido 4e and monoamido 5f and 6f
	were found very active toward the ROP of rac-LA at room temperature (Table 1, entries
	24-28, 30-35); nearly quantitative conversions of the monomer were achieved within a few
	minutes (for 4e, TOF up to 1840 mol(LA)•mol(Y) -1 •h -1 at 25 °C). Without the addition of
	isopropanol, yttrium compound 4e gave PLAs with broad molecular weight distributions (Ð M
	= 2.1, entries 24-26) and number-average molecular weight values generally twice larger

here)

Aluminum-based Initiators. ROP of rac-LA with dimethyl-aluminum 3c and monomethyl-aluminum 3e proceeded at 100 °C in toluene (Table

1

, entries

20-23)

. In general, a good control over the polymerization was achieved with both systems in the presence of isopropanol, as evidenced by the relatively narrow molecular weight distribution of the resulting polymers (Ð M with respect to those calculated from the monomer-to-yttrium ratio. The reactions proceeded even faster in the presence of isopropanol (compare entries 24/27 and 26/28) and all the PLAs formed under those conditions had unimodal narrow molecular distributions (Ð M = 1.21-1.35) and experimental number-average molecular weights (M n ) quite close to the calculated values (entries 27 and 28), indicating a more controlled behavior.

  SiMe 3 )] 220 were prepared as described in the literature. Other starting materials were purchased from Acros, Strem, Alfa and Aldrich and used as received. Racemic lactide (rac-LA) and racemic -butyrolactone (rac-BBL) were received from Aldrich and TCI, respectively. Purification of rac-LA required a three-step procedure involving first a recrystallization from a hot, concentrated iPrOH solution (80 °C), followed by two subsequent recrystallizations in hot toluene (100 °C). Rac-BBL was freshly distilled from CaH 2 under nitrogen and degassed thoroughly by freeze-thaw-vacuum cycles prior to use. After purification, rac-LA and rac-BBL were stored at -30 °C in the glove-box.

	Deuterated solvents were stored over Na/K alloy (benzene-d 6 , toluene-d 8 , THF-d 8 ; >99.5% D, Eurisotop) and vacuum-transferred just before use. CDCl 3 was dried over a mixture of 3 and 4Å molecular sieves. Precursors Ln[N(SiHMe 2 ) 2 ] 3 (THF) (Ln = Sc, Y, La) 19 and on Bruker Avance DRX 400 and AM-500 spectrometers in Teflon-valved NMR tubes at 25 Zn[N(Instrumentation and Measurements. NMR spectra of complexes were recorded ºC unless otherwise indicated.

5b,15,16,18

Experimental Section General Considerations. All manipulations were performed under a purified argon atmosphere using standard Schlenk techniques or in a glovebox (< 1 ppm O 2 , < 5 ppm H 2 O).

Solvents were distilled from Na/benzophenone (THF, Et 2 O) or Na/K alloy (toluene, hexane and pentane) under argon, degassed thoroughly and stored under argon prior to use. 1 H and

13

C NMR chemical shifts are reported in ppm vs.

2-(Methoxymethoxy)-3-(triphenylsilyl)naphthalen-1-yl)picolinaldehyde.

  Pd(PPh 3 ) 4 (0.55 g, 0.47 mmol) and K 3 PO 4 (4.05 g, 19.11 mmol) under argon. Then, dry toluene (100 mL) was added via syringe. The reaction mixture was stirred at room temperature for 30 min, during this time the bright yellow color faded to pale yellow (with insoluble white K 3 PO 4 ). The flask was placed in an oil bath at 115 °C with stirring for 3 days.Then, the reaction mixture was cooled to room temperature and the suspension was filtered through celite with the aid of Et 2 O. Volatiles were removed under vacuum and the resulting residue was purified by recrystallization using an Et 2 O/CH 2 Cl 2 mixture (1:1) to give a solid (3.00 g, 52%).1 H NMR (500 MHz, CDCl 3 , 298 K): 7.88 (s, 1H, aryl-CH), 7.69-7.67 (m, 2H, aryl-CH), 7.64 (d, 3 J H-H = 7.4, 7H, aryl-CH), 7.53-7.47 (m, 3H, aryl-CH), 7.43-7.42 (m, 3H, aryl-CH), 7.39-7.37 (m, 1H, aryl-CH), 3.91 (s, 2H, CH 2 OCH 3 ), 2.62 (s, 3H, CH 2 OCH 3). × 20 mL), and dried over Na 2 SO 4 . Volatiles were removed under vacuum, and the resulting brown oil was chromatographed on silica using CH 2 Cl 2 as eluent. added and the solution was refluxed at 90 °C for 48 h. The reaction mixture was allowed to cool down to room temperature, added to water (50 mL), and extracted with CH 2 Cl 2 (3 × 50 mL). The combined organic layers were dried over magnesium sulfate and evaporated to yield a yellow solid. This solid was dissolved in a mixture of concentrated HCl (20 mL), CHCl 3 (30 mL), and EtOH (40 mL), and the solution was refluxed for 4 h. The reaction mixture was cooled to 0 °C and then carefully diluted with a concentrated solution of NaOH (50 mL). Then, a concentrated solution of NH 4 Cl was added to adjust the pH value to 7-8. The product was extracted with CH 2 Cl 2 (3 × 20 mL), and the combined organic extracts were dried over MgSO 4 and evaporated to afford desired compound as a yellow solid. This material was recrystallized using a Et 2 O/CH 2 Cl 2 mixture (9:1) to afford pure c (0.70 g, 66%). 1H, OH), 8.24(d, 3 J H-H = 8.5, 1H, aryl-CH), 7.92 (t, 3 J H-H = 7.8, 1H, aryl-CH), 7.84 (d, 3 J H-H = 8.9, 2H, aryl-CH), 7.74 (d, 3 J H-H = 7.7, 6H, aryl-CH), 7.67 (d, 3 J H-H = 8.1, 1H, aryl-CH), 7.61-7.57 (m, 2H, aryl-CH), 7.48-7.38 (m, 11H, aryl-CH), 7.29 (t, 3 J H-H = 7.4, 1H, aryl-Cq), 28.0 (CH(CH 3 ) 2 ), 22.4 (CH(CH 3 ) 2 ). Anal. Calcd for C 46 H 42 N 2 OSi: C, 82.84; H, 6.35; N, 4.20. Found: C, 82.80; H, 6.39; N, 4.27.

	126.6 (aryl-CH), 123.8 (aryl-CH), 96.0 (CH 2 OCH 3 ), 84.3 ((BOC(CH 3 ) 2 )), 55.4 (CH 2 OCH 3 ), 25.9 (BOC(CH 3 ) 2 ). Anal. Calcd for C 36 H 37 BO 4 Si: C, 75.52; H, 6.51. Found: C, 75.48; H, 6.54. 2-Bromo-6-(2-(methoxymethoxy)-3-(triphenylsilyl)naphthalen-1-yl)pyridine. An oven-dried 250 mL Schlenk flask, equipped with a stirring bar and a Teflon valve, was charged with 2,6-dimethylpyridine (2.47 g, 10.47 mmol), (3-(methoxymethoxy)-4-(4,4,5,5-99.4 (CH 2 OCH 3 ), 56.0 (CH 2 OCH 3 ). Anal. Calcd for C 35 H 28 BrNO 2 Si: C, 69.76; H, 4.68; N, 2.32. Found: C, 69.72; H, 4.56; N, 2.30. 6-((3-(Methoxymethoxy)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)triphenylsilane (5.00 g, 8.7 mmol) and Na 2 CO 3 (1.91 g, 18.1 mmol) were dissolved in a degassed H 2 O/MeOH mixture (4:1, 60 mL). The resulting solution was added via cannula to a solution of 6-bromopicolinaldehyde (1.35 g, 7.2 mmol) and Pd(PPh 3 ) 4 (416 mg, 0.36 mmol) in degassed toluene (50 mL). The biphasic mixture was heated to 90 °C for 48 h under vigorous stirring. After cooling to room temperature, the organic phase was separated and washed with Et 2 O (3 × 25 mL). The combined organic extracts were washed with H 2 O (3 × dioxaborolan-2-yl)naphthalen-2-yl)triphenylsilane and 6-bromopicolinaldehyde were separated. The remaining fractions were combined and volatiles were removed under vacuum Proligand a. A Schlenk flask was charged with a 1,1'-(pyridine-2,6-diyl)bis(3-(triphenylsilyl)naphthalen-2-ol) 3 (1.00 g, 1.13 mmol) and PhCH 2 K (0.148 g, 1.13 mmol), and THF (ca. 10 mL) was vacuum transferred in at -78 °C. The reaction mixture was gently mmol), PhCH 2 K (0.148 g, 1.13 mmol), Bu 4 NI (0.461 g, 1.25 mmol) and BnBr (148.5 L, 1.25 mmol). The crude material contained ca. 50% of desired product, 1-(6-(2-(benzyloxy)-3-(triphenylsilyl)naphthalen-1-yl)pyridin-2-yl)-3-(triphenylsilyl)naphthalen-2-ol, as judged by (aryl-Proligand f. To a solution of e (1.00 g, 1.49 mmol) in anhydrous, degassed Et 2 O (5 25 mL) and brine (1 The early fractions containing (3-(methoxymethoxy)-4-(4,4,5,5-tetramethyl-1,3,2-to provide 6-(2-(methoxymethoxy)-3-(triphenylsilyl)naphthalen-1-yl)picolinaldehyde as a yellow solid (2.50 g, 63%). 1 H NMR (500 MHz, CDCl 3 , 298 K): 10.19 (s, 1H, CHO), 8.04-8.03 (m, 1H, aryl-CH), 7.96 (s, 1H, aryl-CH), 7.79-7.75 (m, 2H, aryl-CH), 7.70-7.68 (m, 6H, aryl-CH), 7.49-7.40 (m, 13H, aryl-CH), 3.89 (br s, 2H, CH 2 OCH 3 ), 2.55 (s, 3H, CH 2 OCH 3 ). 13 C NMR (125 MHz, CDCl 3 , 298 K): 193.7 (CHO), 157.7 (aryl-Cq), 157.5 6-(2-(Methoxymethoxy)-3-(triphenylsilyl)naphthalen-1-yl)picolinaldehyde (2.50 g, 4.53 mmol) was dissolved in a mixture of concentrated HCl (20 mL), CHCl 3 (30 mL), and EtOH (40 mL), and the solution was refluxed for 4 h. The reaction mixture was cooled to 0 °C and then carefully diluted with a concentrated solution of NaOH (50 mL). Then, a concentrated solution of NH 4 Cl was added to adjust the pH value to 7-8. The product was extracted with CH 2 Cl 2 (3 × 20 mL), and the combined organic extracts were dried over MgSO 4 and evaporated to afford the desired compound as a yellow solid (1.20 g, 52%). 1 H NMR (400 MHz, CDCl 3 , 298 K): 12.01 (s, 1H, OH), 10.09 (s, 1H, CHO), 8.28 (d, 3 J H-H = 8.6 Hz, 1H, aryl-CH), 8.14 (t, 3 J H-H = 8.1, 2H, aryl-CH), 8.00-7.92 (m, 5H, aryl-CH), 7.85 (d, 3 J H-H = 6.5, 5H, aryl-CH), 7.76 (d, 3 J H-H = 7.9, 1H, aryl-CH), 7.73 (d, 3 J H-H = 8.1, 1H, aryl-CH), 7.65 (d, warmed to room temperature and stirred for 2 h at 60 °C. To this mixture, MeI (77.8 L, 1.25 mmol) was added dropwise at -78 °C. The reaction mixture was stirred for 24 h at 60 °C, cooled to room temperature, diluted with water (50 mL), and extracted with CH 2 Cl 2 (3 × 20 mL). The combined organic extracts were dried over MgSO 4 and evaporated to dryness. The crude material contained ca. 50% of the desired product, 1-(6-(2-methoxy-3-(triphenylsilyl)naphthalen-1-yl)pyridin-2-yl)-3-(triphenylsilyl)naphthalen-2-ol, as judged by 129.2 (aryl-CH), 129.1 (aryl-Cq), 128.8 (aryl-Cq), 128.7 (aryl-CH), 127.8 (aryl-CH), 127.7 (aryl-CH), 127.6 (aryl-CH), 125.9 (aryl-Cq), 125.2 (aryl-Cq), 124.7 (aryl-CH), 124.6 (aryl-CH), 124.5 (aryl-CH), 124.4 (aryl-CH), 123.6 (aryl-CH), 122.8 (aryl-CH), 113.0 (aryl-Cq), 60.4 (CH 3 ). Anal. Calcd for C 62 H 47 NO 2 Si 2 : C, 83.28; H, 5.30; N, 1.57. Found: C, 83.35; H, 5.16; N, 1.53. 1 H NMR spectroscopy. This crude material was purified by column chromatography (silica, heptane/toluene (6:4), R f = 0.33). Pure compound b was recovered as a pale yellow powder (0.50 g, 46%). 1 H NMR (400 MHz, CDCl 3 , 298 K): 12.94 (s, 1H, OH), 8.15 (d, 3 J H-H = 8.5, 1H, aryl-CH), 7.84 (s, 1H, aryl-CH), 7.72 (d, 3 J H-H = 8.0, 1H, aryl-CH), 7.68 (s, 1H, aryl-CH), 7.62 (d, 3 J H-H = 7.4, 1H, aryl-CH), 7.63-7.52 (m, 16H, aryl-CH), 7.41-7.37 (m, 1H, aryl-CH), 7.32-7.15 (m, 21H, aryl-CH), 6.88 (t, Proligand c. A solution of 2-bromo-6-(2-(methoxymethoxy)-3-(triphenylsilyl)naphthalen-1-yl)pyridine (1.00 g, 1.66 mmol), (3-methoxynaphthalen-2-yl)boronic acid (0.335 g, 1.66 mmol), Na 2 CO 3 (20 mL of a 2 M solution in water), EtOH (20 mL) and toluene (50 mL) was stirred under argon. After 20 min, Pd(PPh 3 ) 4 (0.095 g, 0.08 mmol) was CH), 121.9 (aryl-CH), 114.7 (aryl-Cq), 106.3 (aryl-CH), 55.0 (CH 3 ). Anal. Calcd for C 44 H 33 NO 2 Si: C, 83.12; H, 5.23; N, 2.20. Found: C, 83.10; H, 5.19; N, 2.28. Proligand d. Using a procedure similar to that described above for c, compound d was obtained from 2-bromo-6-(2-(methoxymethoxy)-3-(triphenylsilyl)naphthalen-1-yl)pyridine (1.00 g, 1.66 mmol), 2-methoxyphenylboronic acid (0.252 g, 1.66 mmol) and Pd(PPh 3 ) 4 (0.095 g, 0.08 mmol). The resulting yellow solid was washed with pentane and OCH 3 ). 13 C NMR (125 MHz, CDCl 3 , 298 K): 159.6 (aryl-Cq), 157.0 (aryl-Cq), 155.8 (aryl-Cq), 155.6 (aryl-Cq), 142.3 (aryl-CH), 137.4 (aryl-CH), 136.5 (aryl-CH), 135.2 (aryl-Cq), 133.3 (aryl-Cq), 130.7 (aryl-CH), 130.4 (aryl-CH), 129.4 (aryl-CH), 129.2 (aryl-CH), 128.9 (aryl-Cq), 127.9 (aryl-Cq), 127.7 (aryl-CH), 127.6 (aryl-CH), 125.3 (aryl-Cq), 124.0 (aryl-CH), 123.5 (aryl-CH), 122.7 (aryl-CH), 121.7 (aryl-CH), 120.8 (aryl-CH), 114.7 (aryl-Cq), 111.5 (aryl-CH), 54.9 (CH 3 ). Anal. Calcd for C 44 H 33 NO 2 Si: C, 82.02; H, 5.33; N, 2.39. Found: C, 82.06; H, 5.40; N, 2.29. Proligand e. CH), 7.92-7.91 (m, 2H, aryl-CH), 7.73 (s, 1H, aryl-CH), 7.59-7.55 (m, 6H, aryl-CH), 7.31-7.18 (m, 12H, aryl-CH), 7.07-7.03 (m, 3H, aryl-CH), 2.87-2.84 (sept, 3 J H-H = 7.4, 2H, CH(CH 3 ) 2 ), 1.07 (d, 3 J H-H = 7.4, 12H, CH(CH 3 ) 2 ). 13 C NMR (100 MHz, CDCl 3 , 298 K): 161.8 (CH=N), 159.4 (aryl-Cq), 156.9 (aryl-Cq), 152.7 (aryl-Cq), 148.3 (aryl-Cq), 142.9 Cq), 133.2 (aryl-Cq), 129.5 (aryl-CH), 129.4 (aryl-CH), 127.9 (aryl-CH), 127.7 (aryl-CH), 125.1 (aryl-Cq), 124.7 (aryl-CH), 123.3 (aryl-CH), 123.2 (aryl-CH), 119.5 (aryl-CH), 113.9 mL) cooled to -30 °C under argon was added phenyllithium (2.25 mL of a 2 M solution in dibutyl ether, 4.49 mmol). After warming to room temperature, the reaction mixture was stirred for 12 h. The reaction was then quenched with aqueous NH 4 Cl. The product was extracted with Et 2 O (3 × 20 mL), and the combined organic extracts were dried over MgSO 4 and evaporated to afford f as a microcrystalline yellow solid (1.00 g, 90%). 1 H NMR (500 MHz, CDCl 3 , 298 K): 11.66 (br s, 1H, OH), 8.17 (d, 3 J H-H = 8.5, 1H, aryl-CH), 7.88 (s, 1H, aryl-CH), 7.79 (d, 3 J H-H = 4.2, 2H, aryl-CH), 7.71-7.68 (m, 7H, aryl-CH), 7.67-7.65 (m, 1H, aryl-CH), 7.50-7.46 (m, 5H, aryl-CH), 7.43-7.39 (m, 6H, aryl-CH), 7.33-7.31 (m, 2H, aryl-124.5 (aryl-CH), 123.7 (aryl-CH), 123.6 (aryl-CH), 123.3 (aryl-CH), 122.8 (aryl-CH), 119.9 (aryl-CH), 113.9 (aryl-Cq), 69.6 (CHPh), 27.7 (CH(CH 3 ) 2 ), 24.1 (CH(CH 3 ) 2 ), 24.0 (CH(CH 3 ) 2 ). Anal. Calcd for C 52 H 48 N 2 OSi: C, 83.83; H, 6.49; N, 3.76. Found: C, 83.90; H, 6.45; N, 3.71. recrystallized from CH CH), 7.06 (t, 3 J H-H = 7.5, 1H, aryl-CH), 6.95 (d, 3 J H-H = 8.3, 1H, aryl-CH), 3.49 (s, 3H, (aryl-CH), 137.8 (aryl-CH), 137.1 (aryl-Cq), 136.6 (aryl-CH), 136.5 (aryl-CH), 134.7 (aryl-Complex 1a. A Schlenk flask was charged with proligand a (0.100 g, 0.112 mmol)

1

H NMR (500 MHz, CDCl 3 , 298 K): 8.00

(d, 3

J H-H = 8.4, 1H, aryl-CH), 7.76 (s, 1H, aryl-CH), 7.61

(d, 3

J H-H = 7.6, 6H, aryl-CH), 7.47-7.44 (m, 1H, aryl-CH), 7.41-7.38 (m, 4H, aryl-CH), 7.36-7.33 (m, 6H, aryl-CH), 7.31-7.28 (m, 1H, aryl-CH), 4.67 (s, 2H, CH 2 OCH 3 ), 2.89 (s, 3H, CH 2 OCH 3 ), 1.48 (s, 12H, BOC(CH 3 ) 2 ).

13

C NMR (125 MHz, CDCl 3 , 298 K): 162.2 (aryl-Cq), 142.3 (aryl-CH), 139.0 (aryl-Cq), 136.4 (aryl-CH), 136.3 (aryl-CH), 135.2 (aryl-Cq), 129.4 (aryl-Cq), 129.2 (aryl-CH), 128.8 (aryl-CH), 128.1 (aryl-CH), 127.6 (aryl-CH), 127.0 (aryl-CH), 126.9 (aryl-Cq), tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-yl)triphenylsilane (5.45 g, 9.52 mmol),

13

C NMR (125 MHz, CDCl 3 , 298 K): 157.9 (aryl-Cq), 157.2 (aryl-Cq), 141.6 (aryl-CH), 141.4 (aryl-Cq), 138.6 (aryl-CH), 136.5 (aryl-CH), 134.8 (aryl-Cq), 134.6 (aryl-Cq), 130.2 (aryl-Cq), 129.5 (aryl-CH), 128.9 (aryl-Cq), 128.5 (aryl-CH), 127.8 (aryl-CH), 127.7 (aryl-CH), 126.7 (aryl-Cq), 126.6 (aryl-CH), 125.9 (aryl-CH), 124.9 (aryl-CH), 124.8 (aryl-CH), (aryl-Cq), 152.6 (aryl-Cq), 141.7 (aryl-CH), 137.3 (aryl-CH), 136.5 (aryl-CH), 134.7 (aryl-Cq), 134.6 (aryl-Cq), 131.6 (aryl-CH), 130.4 (aryl-Cq), 129.6 (aryl-CH), 129.1 (aryl-Cq), 128.7 (aryl-CH), 127.9 (aryl-CH), 127.8 (aryl-CH), 127.1 (aryl-Cq), 125.0 (aryl-CH), 124.6 (aryl-CH), 120.0 (aryl-CH), 99.5 (CH 2 OCH 3 ), 55.9(CH 2 OCH 3 ). Anal. Calcd for C 36 H 29 NO 3 Si: C, 78.37; H, 5.30; N, 2.54. Found: C, 78.42; H, 5.35; N, 2.60.

6-(2-Hydroxy-3-(triphenylsilyl)naphthalen-1-yl)picolinaldehyde.

1 H NMR spectroscopy. This crude material was purified by column chromatography (silica, heptane/EtOAc (9:1), R f = 0.10) and recrystallized from an heptane/EtOAc (9:1) mixture to give, after drying under vacuum, an analytically pure yellow microcrystalline material (0.50 g, 49%). 1 H NMR (400 MHz, CDCl 3 , 298 K): 12.87 (br s, 1H, OH), 8.22 (d, 3 J H-H = 8.6, 1H, aryl-CH), 7.91-7.87 (m, 2H, aryl-CH), 7.78 (s, 1H, aryl-CH), 7.67 (s, 1H, aryl-CH), 7.64-7.60 (m, 2H, aryl-CH), 7.56-7.51 (m, 12H, aryl-CH), 7.44-7.39 (m, 2H, aryl-CH), 7.32-7.16 (m, 22H, aryl-CH), 2.29 (s, 3H, OCH 3 ). 13 C NMR (100 MHz, CDCl 3 , 298 K): 160.5 (aryl-Cq), 160.4 (aryl-Cq), 156.9 (aryl-Cq), 154.1 (aryl-Cq), 142.8 (aryl-CH), 141.1 (aryl-CH), 137.2 (aryl-CH), 136.6 (aryl-CH), 136.4 (aryl-CH), 134.8 (aryl-Cq), 134.7 (aryl-Cq), 134.6 (aryl-Cq), 133.2 (aryl-Cq), 130.2 (aryl-Cq), 129.4 (aryl-CH), 129.3 (aryl-CH), Proligand b. Using a procedure similar to that described above for a, proligand b was obtained 1,1'-(pyridine-2,6-diyl)bis(3-(triphenylsilyl)naphthalen-2-ol) (1.00 g, 1.13 3 J H-H = 7.3, 1H, OCH 2 Ph), 6.78 (t, 3 J H-H = 7.5, 2H, OCH 2 Ph), 6.23 (d, 3 J H-H = 7.3, 2H, OCH 2 Ph), 3.81 (s, 2H, OCH 2 Ph). 13 C NMR (100 MHz, CDCl 3 , 298 K): 160.4 (aryl-Cq), 159.4 (aryl-Cq), 156.5 (aryl-Cq), 154.0 (aryl-Cq), 142.8 (aryl-CH), 141.4 (aryl-CH), 137.5 (aryl-Cq), 137.1 (aryl-CH), 136.6 (aryl-CH), 136.5 (aryl-CH), 134.8 (aryl-Cq), 134.7 (aryl-Cq), 134.6 (aryl-Cq), 133.2 (aryl-Cq), 130.3 (aryl-Cq), 129.5 (aryl-CH), 129.4 (aryl-CH), 129.3 (aryl-CH), 129.0 (aryl-Cq), 128.9 (aryl-Cq), 128.7 (aryl-CH), 127.8 (aryl-CH), 127.7 (aryl-CH), 127.6 (aryl-CH), 127.3 (aryl-CH, OCH 2 Ph), 127.1 (aryl-Cq, OCH 2 Ph), 126.6 (aryl-CH, OCH 2 Ph), 126.2 (aryl-CH, OCH 2 Ph), 125.2 (aryl-Cq), 125.1 (aryl-CH), 124.7 (aryl-CH), 124.6 (aryl-CH), 124.5 (aryl-CH), 123.7 (aryl-CH), 122.9 (aryl-CH), 113.3 (aryl-Cq), 75.9 (OCH 2 Ph). Anal. Calcd for C 68 H 51 NO 2 Si 2 : C, 84.17; H, 5.30; N, 1.44. Found: C, 84.55; H, 5.22; N, 1.47. Yellow crystals of b suitable for X-ray diffraction analysis were obtained by prolonged crystallization from CHCl 3 at room temperature. 1 H NMR (400 MHz, CDCl 3 , 298 K): 12.56 (br s, 1H, OH), 8.25 (d, 3 J H-H = 8.5, 1H, aryl-CH), 8.06 (s, 1H, aryl-CH), 7.95 (t, 3 J H-H = 7.8, 1H, aryl-CH), 7.87 (d, 3 J H-H = 7.9, 1H, aryl-CH), 7.83-7.81 (m, 2H, aryl-CH), 7.74 (d, 3 J H-H = 6.8, 7H, aryl-CH), 7.69-7.67 (m, 2H, aryl-CH), 7.49-7.46 (m, 2H, aryl-CH), 7.44-7.37 (m, 10H, aryl-CH), 7.29 (t, 3 J H-H = 7.4, 1H, aryl-CH), 7.18 (s, 1H, aryl-CH), 3.57 (s, 3H, OCH 3 ). 13 C NMR (100 MHz, CDCl 3 , 298 K): 159.6 (aryl-Cq), 155.9 (aryl-Cq), 155.5 (aryl-Cq), 155.2 (aryl-Cq), 142.3 (aryl-CH), 137.5 (aryl-CH), 136.5 (aryl-CH), 135.2 (aryl-CH), 135.1 (aryl-CH), 134.8 (aryl-Cq), 133.2 (aryl-Cq), 130.7 (aryl-CH), 130.6 (aryl-CH), 129.5 (aryl-Cq), 129.4 (aryl-CH), 129.2 (aryl-CH), 128.8 (aryl-Cq), 128.6 (aryl-Cq), 128.1 (aryl-CH), 127.7 (aryl-CH), 127.1 (aryl-CH), 126.4 (aryl-CH), 125.4 (aryl-Cq), 124.3 (aryl-CH), 124.2 (aryl-CH), 123.5 (aryl-CH), 122.8 (aryl-2 Cl 2 to afford d (0.91 g, 93%). 1 H NMR (400 MHz, CDCl 3 , 298 K): 12.55 (s, A solution of 6-(2-hydroxy-3-(triphenylsilyl)naphthalen-1yl)picolinaldehyde (1.20 g, 2.36 mmol) and 2,6-diisopropylaniline (0.54 g, 3.07 mmol) in THF (50 mL) containing 3Å molecular sieves and a catalytic amount of TsOH was heated to reflux under argon for 12 h. After filtration and removal of the volatiles under vacuum, the crude material was recrystallized from a CH 2 Cl 2 /pentane mixture (1:1) to afford e as a microcrystalline yellow solid (1.20 g, 76%). 1 H NMR (400 MHz, CDCl 3 , 298 K): 11.86 (br s, 1H, OH), 8.19 (s, 1H, CH=N), 8.15-8.12 (m, 1H, aryl-CH), 8.05 (d, 3 J H-H = 8.5, 1H, aryl-CH), 7.23-7.20 (m, 3H, aryl-CH), 7.05-7.02 (m, 3H, aryl-CH), 5.24 (s, 1H, CHPh), 2.95-2.90 (sept, 3 J H-H = 6.8, 2H, CH(CH 3 ) 2 ), 1.05 (d, 3 J H-H = 6.8, 6H, CH(CH 3 ) 2 ), 1.02 (d, 3 J H- H = 6.7, 6H, CH(CH 3 ) 2 ). 13 C NMR (125 MHz, CDCl 3 , 298 K): 161.1 (aryl-Cq), 159.7 (aryl-Cq), 156.7 (aryl-Cq), 142.4 (aryl-CH), 142.1 (aryl-Cq), 141.9 (aryl-Cq), 141.1 (aryl-Cq), 137.4 (aryl-CH), 136.6 (aryl-CH), 134.8 (aryl-Cq), 133.1 (aryl-Cq), 129.4 (aryl-CH), 129.2 (aryl-CH), 128.9 (aryl-CH), 128.7 (aryl-CH), 128.6 (aryl-CH), 128.5 (aryl-CH), 127.6 (aryl-CH), 127.4 (aryl-CH), 127.2 (aryl-CH), 127.1 (aryl-CH), 126.1 (aryl-Cq), 125.4 (aryl-Cq),

  H NMR (500 MHz, toluene-d 8 , 253 K): 8.31 (s, 1H, aryl-CH), 8.07 (s, 1H, aryl-CH), 7.96-7.94 (m, 6H, aryl-CH), 7.91 (d, 3 J H-H = 8.5, 1H,

	aryl-CH), 7.79 (d, 3 J H-H = 8.3, 1H, aryl-CH), 7.74 (d, 3 J H-H = 7.2, 6H, aryl-CH), 7.37 (d, 3 J H-H
	= 8.1, 1H, aryl-CH), 7.33 (d, 3 J H-H = 7.9, 1H, aryl-CH), 7.26 (d, 3 J H-H = 8.1, 1H, aryl-CH),
	7.22-7.16 (m, 14H, aryl-CH), 7.05 (t, 3 J H-H = 7.6, 8H, aryl-CH), 6.77 (t, 3 J H-H = 7.9, 1H, aryl-
	CH), 6.45 (d, 3 J H-H = 7.5, 1H, aryl-CH), 2.34 (s, 3H, OCH 3 ), 0.45 (t, 3 J H-H = 8.1, 3H,
	ZnCH 2 CH 3 ), -0.06--0.14 (m, 1H, ZnCH 2 CH 3 ), -0.53--0.46 (m, 1H, ZnCH 2 CH 3 ). 13 C{ 1 H}
	NMR (125 MHz, toluene-d 8 , 298 K): 169.3 (aryl-Cq), 158.1 (aryl-Cq), 143.8 (aryl-CH),
	142.2 (aryl-CH), 137.0 (aryl-CH), 136.8 (aryl-CH), 130.1 (aryl-CH), 129.5 (aryl-CH), 129.2
	(aryl-CH), 128.9 (aryl-CH), 128.8 (aryl-CH), 128.1 (aryl-CH), 128.0 (aryl-CH), 127.7 (aryl-

CH), 127.2 (aryl-CH), 127.0 (aryl-CH), 125.7 (aryl-CH), 124.5 (aryl-CH), 124.2 (aryl-CH), 122.7 (aryl-CH), 121.1 (aryl-CH), 113.7 (aryl-CH), 59.2 (OCH 3 ), 11.8 (ZnCH 2 CH 3 ), -1.8 (ZnCH 2 CH 3 ) Anal. Calcd for C 64 H 51 NO 2 Si 2 Zn: C, 77.83; H, 5.20; N, 1.42. Found: C, 77.95; H, 5.02; N, 1.53. Yellow crystals of 1a suitable for X-ray diffraction analysis were obtained by prolonged crystallization from a C 7 H 8 /heptane mixture (1:1) at room temperature.

Table 1 .

 1 Cq), 136.1 (aryl-Cq), 132.9 (aryl-CH), 131.8 (aryl-Cq), 130.7 (aryl-Cq), 129.7 (aryl-CH), 129.6 (aryl-Cq), 129.5 (aryl-Cq), 129.2 (aryl-CH), 128.9 (aryl-CH), 128.4 (aryl-CH), 128.1 (aryl-CH), 128.0 (aryl-CH), 127.9 (aryl-CH), 127.8 (aryl-Cq), 127.4 (aryl-CH), 127.3 (aryl-2H, aryl-CH), 6.73(d, 3 J H-H = 8.0, 1H, aryl-CH), 6.56(d, 3 J H-H = 7.5, 1H, aryl-CH), 3.04 (s, 3H, OCH 3 ), -0.04 (s, 18H, ZnN(SiMe 3 ) 2 ).13 C NMR (125 MHz, C 6 D 6 , 298 K): 171.4 (aryl-Cq), 157.9 (aryl-Cq), 155.4 (aryl-Cq), 152.5 (aryl-Cq), 144.9 (aryl-CH), 138.0 (aryl-1H, aryl-CH), 6.44(d, 3 J H-H = 7.8, 1H, aryl-CH), 4.81 (q, 3 J H-H = 6.0, 1H, CHCH 3 ), 3.70 (sept, 3 J H-H = 6.6, 1H, CH(CH 3 ) 2 ), 3.40 (sept, 3 J H-H = 6.6, 1H, CH(CH 3 ) 2 ), 1.36(d, 3 J H-H = 6.6, 3H, CH(CH 3 ) 2 ), 1.21(d, 3 J H-H = 6.6, 3H, CH(CH 3 ) 2 ), 1.20(d, 3 J H-H = 6.6, 3H, CH(CH 3 ) 2 ), Si), -22.7 (br s, 2Si, SiHMe 2 ), -22.8 (br s, 2Si, SiHMe 2 ).[START_REF]1 J Si-H = 165, 2Si)[END_REF] Si NMR (79 MHz, C 6 D 6 , 333 K): -22.7 (d sept, 1 J Si-H = 165, 2 J Si-H = 6.8, 2Si), -22.8 (d sept, 1 J Si-H = 165, 2 J Si-H = 6.8, 2Si). for PHB at 1.49 ppm and for BBL at 1.16 ppm. The microstructure of PHBs was determined by13 C NMR spectroscopy (methylene region) at 20 °C in CDCl 3 on a Bruker AC-500 spectrometer. Bruker APEX CCD diffractometer with graphite-monochromatized MoK α radiation (λ = 0.71073 Å). A combination of ω and φ scans was carried out to obtain at least a unique data set. The crystal structures were solved by direct methods, remaining atoms were located from difference Fourier synthesis followed by full-matrix least-squares refinement based on F2 (programs SIR97 and SHELXL-97)22 with the aid of the WINGX program.23 In most cases, many hydrogen atoms could be found from the Fourier difference analysis. Other hydrogen atoms were placed at calculated positions and forced to ride on the attached atom. Chem. Soc. Rev. 2010, 39, 486. (c) Carpentier, J.-F. Macromol. Rapid Commun. 2010, 31, 1696. (d) Dijkstra, P. J.; Du, H.; Feijen, J. Polym. Chem. 2011, 2, 520. Grunova, E.; Kirillov, E.; Roisnel, T.; Carpentier, J.-F. Dalton Trans. 2010, 39, 6739. (b) Klitzke, J. S.; Roisnel, T.; Kirillov, E.; Casagrande Jr, O.; Carpentier, J.-F. ROP of racemic lactide promoted by complexes 1a,

	1 H

(aryl-CH), 138.0 (aryl-CH), 137.6 (aryl-Cq), 137.4 (aryl-CH), 137.3 (aryl-CH), 136.9 (aryl-Complex 1d. Using a procedure similar to that described above for 1a, compound 1d was obtained from proligand d (0.100 g, 0.170 mmol) and ZnEt 2 (0.19 mL of a 1.0 M solution in toluene, 0.19 mmol) and isolated as a yellow microcrystalline material (0.080 g, 69%).

1

H NMR (500 MHz, C 6 D 6 , 298 K): 8.11 (s, 1H, aryl-CH), 7.98-7.96 (m, 6H, aryl-CH), 7.86 (d, 3 J H-H = 8.5, 1H, aryl-CH), 7.44 (d, 3 J H-H = 8.2, 1H, aryl-CH), 7.36 (d, 3 J H-H = 8.0, 1H, aryl-CH), 7.21-7.20 (m, 8H, aryl-CH), 7.17 (d, 3 J H-H = 7.9, 1H, aryl-CH), 7.09 (d, 3 J H-H = 7.3, 1H, aryl-CH), 7.02 (d, 3 J H-H = 7.6, 1H, aryl-CH), 6.98 (d, 3 J H-H = 7.1, 1H, aryl-1 H NMR (500 MHz, C 6 D 6 , 298 K): 8.26 (d, 3

J H-H = 8.5, 1H, aryl-CH), 8.01 (s, 1H, aryl-CH), 7.87-7.85 (m, 2H, aryl-CH), 7.81-7.79 (m, 6H, aryl-CH), 7.63 (d, 3 J H-H = 7.CH), 136.5 (aryl-CH), 135.1 (aryl-Cq), 129.8 (aryl-CH), 129.1 (aryl-CH), 128.7 (aryl-CH), 128.3 (aryl-Cq), 128.1 (aryl-CH), 127.7 (aryl-CH), 127.6 (aryl-CH), 127.2 (aryl-CH), 127.1 3 THF (0.075 g, 0.134 mmol), and toluene (ca. 10 mL) was vacuum transferred in. The reaction mixture was stirred 12 h at 50 °C, then filtered and evaporated under vacuum. The residue was washed with pentane (10 mL) and dried under vacuum to give 5f as an orange microcrystalline material (0.110 g, 81%). 1 H NMR (400 MHz, toluened 8 , 298 K): 8.09 (d, 3 J H-H = 8.6, 1H, aryl-CH), 7.93 (s, 1H, aryl-CH), 7.(aryl-CH), 136.4 (aryl-Cq), 129.3 (aryl-CH), 129.2 (aryl-CH), 129.1 (aryl-CH), 128.9 (aryl-CH), 128.5 (aryl-CH), 128.0 (aryl-CH), 127.7 (aryl-Cq), 127.4 (aryl-CH), 127.2 (aryl-CH), resonances The hydrogen atom contributions were calculated but not refined. All non-hydrogen atoms were refined with anisotropic displacement parameters. The locations of the largest peaks in the final difference Fourier map calculation as well as the magnitude of the residual electron densities were of no chemical significance. Crystal data and details of data collection and structure refinement for proligands a, b . CHCl 3 , c, d, e . C 5 H 12 and complexes 1a . 0.2 A particular case when two stereocontrol mechanisms are operational at the same time has been reported to result in gradient multiblock PLAs, see: Pilone, A.; Press, K.; Goldberg, I.; Kol, M.; Mazzeo, M.; Lamberti, M. J. Am. Chem. Soc. 2014, 136, 2940. 3 Kirillov, E.; Roisnel, T.; Razavi, A.; Carpentier, J.-F. Organometallics 2009, 28, 5036.

4 For leading references to the use of group 13 complexes based on closely related Nand/or O-based tridentate dianionic ligands in the ROP of lactide/cyclic carbonates, see: (a) Hild, F.; Brelot, L.; Dagorne, S. Organometallics 2011, 30, 5457. (b) Hild, F.; Dagorne, S. Organometallics 2012, 31, 1189. (c) Hild, F.; Neehaul, N.; Bier, F.; Wirsum, M.; Gourlaouen, C.; Dagorne, S. Organometallics 2013, 32, 587.

5 (a) 6 Related ligand systems have been recently employed for the preparation of complexes of magnesium, calcium and aluminum, see: (a) Yi, W.; Ma, H. Inorg. Chem. 2013, 52,

1c, 1d, 2c, 2d, 2e, 3c, 3e', 4e

  Polymerization conditions otherwise stated: [rac-LA] 0 = 1.0 M, solvent = toluene. b Reaction times were not necessarily optimized. c Monomer conversion determined by 1 H NMR spectroscopy (CDCl 3 , 298 K). d Theoretical molecular weight calculated using M n,theo = conv(LA) × [rac-LA] 0 /[M or iPrOH] × M LA . e Determined by 1 H NMR spectroscopy.f Experimental molecular weight determined by SEC vs. polystyrene standards and corrected by a factor of 0.58; Ð M = M w /M n . g P r is the probability racemic linkage between monomer units, as determined from the methine region of the homonuclear decoupled 1 H NMR spectrum. h Carried out in THF.

	and 4---29 -6f. a 4f Entry Complex 30 5f 31 g 5f	100:1:0 [LA] 0 /[M] /[iPrOH] 0 a 100:1:0 100:1:0	60 25 Temp (°C) 25	1 Time 1.67 b (h) 1	68 Conv. 93 c (%) 83	9.8 M n,theo 13.4 (g•mol -1 ) d (× 10 3 ) 11.9	11.6 M n,NMR e 11.9 (g•mol -1 ) (× 10 3 ) nd	11.0 M n,SEC f 12.1 (g•mol -1 ) (× 10 3 ) 15.2	1.47 1.50 Ð M f 1.54	0.58 0.60 g P r 0.69
	1 32	1a 5f	100:1:0 500:1:0	25 25	24 6	0 44	-31.7	nd nd	-28.2	-1.60	-0.58
	2 33	1a 5f	100:1:0 100:1:1	100 25	48 0.83	0 98	-14.1	nd 16.4	-15.8	-1.43	-0.57
	3 34	1a 6f	100:1:5 100:1:0	100 25	48 0.25	90 99	2.6 14.3	6.5 nd	6.2 14.2	1.31 1.98	0.54 0.69
	4 35	1a 6f	1,000:1:5 100 100:1:1 25	144 0.13	23 98	6.6 14.2	9.6 13.8	9.9 13.3	1.33 1.57	0.56 0.68
	5 h	1c	100:1:0	60	4	91	13.1	nd	42.3	2.12	0.75
	6	1c	100:1:0	80	0.5	92	13.2	nd	20.8	1.70	0.65
	7	1d	100:1:0	80	0.33	82	11.8	nd	21.2	1.56	0.66
	8	2c	100:1:0	25	0.33	90	12.9	nd	11.7	1.68	0.72
	9	2c	250:1:0	25	0.5	84	30.3	nd	27.7	1.91	0.73
	10	2c	500:1:0	25	0.66	57	41.1	nd	40.1	1.88	0.76
	11	2c	1,000:1:0	25	1	38	54.7	nd	58.8	1.92	0.74
	12	2c	2,000:1:0	25	1.75	77	222.2	nd	216.5	2.04	0.73
	13	2c	100:1:1	25	7	0	-	-	-	-	-
	14	2c	1,000:1:1 100	0.13	45	64.8	nd	30.6	1.46	0.65
	15	2d	100:1:0	25	0.5	36	5.2	5.7	5.4	1.32	0.75
	16	2e	100:1:0	25	0.33	99	14.3	nd	13.8	1.11	0.71
	17	2e	500:1:0	25	1.33	85	61.2	nd	54.5	1.11	0.72
	18	2e	100:1:1	25	24	0	-	-	-	-	-
	19	2e	500:1:1	25	24	0	-	-	-	-	-
	20	3c	100:1:0	100	24	84	12.1	nd	29.9	1.54	0.50
	21	3c	100:1:2	100	16	91	13.1	13.0	12.6	1.37	0.54
	22	3e	100:1:0	100	24	92	13.2	12.9	13.4	1.17	0.50
	23	3e	100:1:1	100	14	80	11.5	12.2	11.9	1.14	0.50
	24	4e	100:1:0	25	0.17	99	14.3	nd	27.5	2.13	0.80
	25 h	4e	100:1:0	25	0.17	99	14.3	nd	33.9	2.11	0.79
	26	4e	500:1:0	25	0.5	96	69.2	nd	140.3	2.10	0.80
	27	4e	100:1:2	25	0.08	>99	14.4	10.9	11.5	1.21	0.78
	28	4e	500:1:2	25	0.25	92	66.3	nd	56.1	1.35	0.79

a

Table 2 .

 2 ROP of racemic -butyrolactone promoted by complexes 2c, 2e, 3c, 3e', 4e and 4----6f. a All reactions performed with [rac-BL] 0 = 1.0 M. b Reaction times were not necessarily optimized. c BL conversion to PHB determined by 1 H NMR spectroscopy (CDCl 3 , 298 K) on the crude reaction mixture. d Theoretical molecular weight calculated using M n, theo = conv(BL) × [rac-BL] 0 /[M or iPrOH] × M BL . e Experimental (uncorrected) molecular weight determined by SEC in THF; Ð M = M w /M n . f Experimental (uncorrected) molecular weight determined by SEC in CHCl 3 ; Ð M = M w /M n . g P r is the probability of racemic linkage between monomer units and is determined by 13 C{ 1 H} NMR spectroscopy.

	Entry Complex	[BL] 0 /[M] /[iPrOH] 0 a	Temp (°C)	Time b (h)	Conv. c (%)	M n,theo (g•mol -1 ) d (× 10 3 )	e M n,SEC (g•mol -1 ) (× 10 3 )	Ð M e	P r g
	1	2c	100:1:0	25	24	0	-	-	-	-
	2	2c	100:1:0	80	4.5	>99	8.6	19.2	1.22	nd
	3	2c	500:1:0	60	14	70	30.1	39.3	1.07 0.56
	4	2c	500:1:0	80	19	>99	43.0	55.9	1.07 0.56
	5 h	2c	500:1:0	80	28	52	22.4	25.6	1.13 0.56
	6	2e	100:1:0	60	4	85	7.3	15.2	1.23 0.50
	7	3c	100:1:0	60	24	0	-	-	-	-
	8	3c	100:1:2	100	24	0	-	-	-	-
	9	3e	100:1:0	100	24	0	-	-	-	-
	10	4e	100:1:0	25	0.08	73	6.3	289.3 f	1.54 f 0.56
	11	4f	100:1:0	60	24	0	-	-	-	-
	12	5f	100:1:0	25	1	traces	nd	nd	nd	nd
	13	5f	100:1:0	25	24	97	8.3	13.1	1.89 0.42
	14	6f	100:1:0	25	24	81	6.9	11.1	1.48 0.66

a h Carried out in THF.

J H-H = 7.4, 1H, aryl-CH), 7.55-7.45 (m, 5H, aryl-CH), 7.39-7.32 (m, 2H, aryl-CH).

Acknowledgments. We thank the University of Rennes 1 and CNRS for partial support of this work. We thank S. Sinbandhit (University of Rennes 1) for his help in conducting some NMR experiments.

Complex 3c. Using a procedure similar to that described above for 1a, compound 3c was obtained from proligand c (0.100 g, 0.157 mmol) and AlMe 3 (0.17 mL of a 1.0 M solution in toluene, 0.17 mmol) and isolated as a yellow microcrystalline material (0.096 g, 88%). 1 H NMR (500 MHz, C 6 D 6 , 298 K): 8.31 (s, 1H, aryl-CH), 7.92-7.90 (m, 6H, aryl-CH), 7.51 (d, 3 J H-H = 8.3, 2H, aryl-CH), 7.41 (d, 3 J H-H = 8.0, 2H, aryl-CH), 7.23 (q, 3 J H-H = 7.4, 2H, aryl-CH), 7.14-7.12 (m, 8H, aryl-CH), 7.09-7.06 (m, 4H, aryl-CH), 6.98 (d, 3

Reaction of proligand e with AlMe 3 . Synthesis of Complex 3e' and Isolation of X-ray Suitable Crystals of 3e''.

A Schlenk flask was charged with proligand e (0.100 g, 0.149 mmol) and toluene (ca. 10 mL) was transferred in. AlMe 3 (0.16 mL of a 1.0 M solution in toluene, 0.165 mmol) was added to the reaction mixture at -78 °C. The reaction mixture was stirred at room temperature overnight. The solution was filtered and volatiles were evaporated under vacuum affording 3e' as a pale yellow microcrystalline powder (0.098 g, 91%). 1 1, entry 5), in a glovebox, a Schlenk flask was charged with a solution of complex 1c (10.0 mg, 13.7 µmol) in toluene (1.0 mL). To this solution, rac-lactide (0.197 g, 1.37 mmol, 100 equiv vs. Zn) was added rapidly. The mixture was immediately stirred with a magnetic stirrer bar at 80 °C for 30 min. Aliquots of the crude material were periodically sampled by pipette for determining the monomer conversion by 1 H NMR spectroscopy in CDCl 3 , from the integration (Int.) ratio Int. polymer /[Int. polymer +Int. monomer ], using the methyl hydrogen resonances for PLA at 1.49 ppm and for LA at 1.16 ppm. The reaction was quenched with a solution of H 2 O in THF (ca. 1 mL, 10 wt-%), and the polymer was precipitated with an excess amount of methanol (ca. 100 mL). The polymer was then filtered and dried under vacuum to a constant weight.

The microstructure of PLAs was determined by homodecoupling 1 H NMR spectroscopy (methine region) at 20 °C in CDCl 3 on a Bruker AC-500 spectrometer.

General Procedure for Polymerization of rac--Butyrolactone. In a typical experiment (Table 2, entry 2), in a glovebox, a Schlenk flask was charged with a solution of complex 2c (10.0 mg, 11.6 µmol) in toluene (1.1 mL). To this solution, rac--butyrolactone (0.99 g, 1.16 mmol, 100 equiv vs. Zn) was added rapidly. The mixture was immediately stirred with a magnetic stirrer bar at 80 °C for 4.5 h. The reaction was processed and workedup similarly to that described above for lactide polymerization. Monomer conversions were calculated from 1 H NMR spectra of the crude reaction mixtures in CDCl 3 , from the integration (Int.) ratio Int. polymer /[Int. polymer +Int. monomer ], using the methylene hydrogen Supporting Information available. Electronic supplementary information (ESI) available:

Representative 1 H and 13 C{ 1 H} NMR spectra and crystallographic details of the prepared proligands, complexes and polymers. CCDC 1020173, 1020174, 1020175, 1020176,

Highlights:

-New tridentate ortho-Ph 3 Si-substituted naphthol-pyridine ligands were synthesized -Zn, Al, Y and La complexes were prepared -Some of these complexes exhibit high activity in ROP of lactide and β-butyrolactone -Good molecular weight control and narrow distributions are achieved