Supporting Information

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 205 Supporting Information Synthesis and Structures of N-Arylcyano-β-diketiminate Zinc Complexes and Adducts, their Application in Ring Opening Polymerization of L-lactide Oleksandra S. Trofymchuk, a Constantin G. Daniliuc, b Gerald Kehr, b Gerhard Erker,* b and Rene S. Rojas* a Table of contents Synthesis and Characterization of compounds... Zn 2 (L ) 2 (OH) 2 ( a )...22 Crystallography Characterization of compounds...23 H NMR spectra of PLLA formation...26 H NMR spectrum of partially dissociated complex 2.27 H NMR spectrum of PLLA...27 MALDI-TOF spectrum of PLLA...28 PLLA SEC characterization..28. Synthesis and Characterization of compounds Preparation of ZnL N(SiMe 3 ) 2,. Zn{N(SiMe 3 ) 2 } 2 (28.9 mg, 278. mmol) and L H (00 mg, 278. mmol) were dissolved in toluene and stirred at 80 o C for 2 h. Evaporation of the solvent yielded a pale yellow, airsensitive solid, that was washed with 3-4 ml cold pentane, and dried in vacuo. Yield: 0 mg (88.3 mmol, 68 %). Single crystals for X-ray crystallography were grown by layering pentane onto a toluene solution of compound () at-30 o C.

2 H NMR (600 MHz, C 6 D 6, 299 K) 3 C {H} (00 MHz, C 6 D 6, 299 K) 2

3 H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm = 0.03 (bd, 8H, N(SiMe 3 ) 2 ),.6 (d, J =.6 Hz, 6H, CH(CH 3 ) 2 ),.46 (d, 6H, J =.6 Hz, CH(CH 3 ) 2 ),.64 (s, 3H, Me),.65 (s, 3H, Me), 3.33 (bs, 2H, CH(CH 3 ) 2 ), 4.88 (s, H, CH), 6.59 (m, H, Ar-H), 6.99 (m, 2H, Ar-H), 7.09 (m, H, Ar-H), 7.3 (m, 3H, Ar-H j,j,k ). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = 5.22 (N(Si(CH 3 ) 3 ) 2 ), (CH(CH 3 ) 2 ), 24.5 (CH(CH 3 ) 2 ), (Me), (CH(CH 3 ) 2 ), (CH), 0.77 (Ar-C), 7.67 (C N), (Ar-CH), (Ar-CH), (Ar-CH), (Ar-C), 28.5 (Ar-C), (Ar-CH), 33.3 (Ar-CH), (Ar-C), (Ar-C), 67.0 (C=N), 7.69 (C=N). GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) =.6/ 3.33 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 3.33/.6,.46 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 6.59/ 6.99, 7.09 (Ar-H/ Ar-H, Ar-H), 6.99/ 6.59 (Ar-H/ Ar-H), 7.09/ 6.59, 6.99 (Ar-H/ Ar-H, Ar-H). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.03/ 5.22 (N(Si(CH 3 ) 3 ) 2 / N(Si(CH 3 ) 3 ) 2 ),.6/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.46/ 24.5 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.64/ (Me/ Me),.65/ (Me/ Me), 3.33/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 4.88/ (CH/ CH), 6.59/ (Ar-H/ Ar-CH), 6.99/ 27.59, (Ar- H/ Ar-CH, Ar-CH), 7.09/ 33.3 (Ar-H/ Ar-CH), 7.3/ (Ar-H/ Ar-CH). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.03/ 5.22 (N(Si(CH 3 ) 3 ) 2 / N(Si(CH 3 ) 3 ) 2 ),.6/ 23.58, 24.79, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH, Ar- C),.46/ 24.5, 24.79, 43.87, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH, Ar-C, Ar-C),.64/ 97.22, 67.0 (Me/ CH, C=N),.65/ 97.22, 7.69 (Me/ CH, C=N), 4.88/ 24.79, 43.87, 52.59, 67.0, 7.69 (CH/ Me, Ar-C, Ar-C, C=N, C=N), 6.59/ 0.77, (Ar-H/ Ar-C, Ar- CH), 6.99/ 27.59, (Ar-H/ Ar-CH, Ar-CH), 6.99/ 7.67, 25.34, 33.3, (Ar-H/ C N, Ar-CH, Ar-CH, Ar-C), 7.09/ 7.67, 33.3, (Ar-H/ C N, Ar-CH, Ar- C), 7.3/ 23.58, 24.5, 25.34, (Ar-H/ CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH, Ar-C). 29 Si, { H} (75 MHz, C 6 D 6, 299 K): δ = 0.05 ppm. DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.6/.46,.64,.65, 3.33, 7.3 (CH(CH 3 ) 2 / CH(CH 3 ) 2, Me, Me, CH(CH 3 ) 2, Ar-H),.46/ 3.33, 7.3 (CH(CH 3 ) 2 / CH(CH 3 ) 2, Ar-H),.64/ 3.33, 4.88, 6.59 (Me/ CH(CH 3 ) 2, CH, Ar-H), 6.59/ 6.99, 7.09 (Ar-H/ Ar-H, Ar- H), 6.99/ 7.09 (Ar-H/ Ar-H), 7.3/.6,.46 (Ar-H/ CH(CH 3 ) 2, CH(CH 3 ) 2 ). 3

4 D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.6/.46, 3.33 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.46/.6, 3.33 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 6.59/ 6.99, 7.09 (Ar-H/ Ar-H, Ar-H). IR (KBr): ν/cm - = 2225 (ν (C N), s). Elemental analysis (%) C 30 H 46 N 4 Si 2 Zn (M = g/mol): calculated C 6.67, H 7.94, N 9.59; found C 62.3, H 7.47, N Preparation of ZnL 2 N(SiMe 3 ) 2, 2. Zn{N(SiMe 3 ) 2 } 2 (54.3 mg, mmol) and L 2 H (00 mg, mmol) were dissolved in toluene and stirred at 80 o C for 2 h. Evaporation of the solvent yielded a yellow, airsensitive solid, that was washed with 5 ml cold pentane, and dried in vacuo. Yield: 3 mg (249.5 mmol, 75 %). Single crystals for X-ray crystallography were grown by layering pentane onto a toluene solution of compound (2) at-30 o C. 4

5 H NMR (600 MHz, C 6 D 6, 299 K) 3 C {H} (00 MHz, C 6 D 6, 299 K) H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm = 0.00 (s, 8H, N(SiMe 3 ) 2 ),.59 (s, 6H, Me), 4.85 (s, H, CH ), 6.54 (m, 2H, Ar-H), 6.70 (m, 2H, Ar-H), 6.89 (m, 2H, Ar-H), 7.09 (m, 2H, Ar-H). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = 5.24 (N(Si(CH 3 ) 3 ) 2 ), (Me), (CH), 0.5 (Ar-C), 7.42 (C N), (Ar-CH), (Ar-CH), (Ar-C), (Ar-C), (Ar-CH), (Ar-CH), 5.86 (Ar-C), 69.3 (C=N). GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) = 6.54/ 6.89, 7.09 (Ar-CH/ Ar-CH, Ar-CH), 6.70/ 6.89 (Ar-CH/ Ar-CH), 6.89/ 6.54, 6.70 (Ar-H/ Ar-H, Ar-H), 7.09/ 6.54 (Ar-H/ Ar-H). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.00/ 5.24 (N(Si(CH 3 ) 3 ) 2 / N(Si(CH 3 ) 3 ) 2 ),.59/ (Me/ Me), 4.85/ (CH/ CH), 6.54/ (Ar-H/ Ar-CH), 6.70/ (Ar-H/ Ar-CH), 6.89/ (Ar-H/ Ar-CH), 7.09/ (Ar-H/ Ar-CH). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.00/ 5.24 (N(Si(CH 3 ) 3 ) 2 / N(Si(CH 3 ) 3 ) 2 ),.59/ 97.76, 69.3 (Me/ CH, C=N), 4.85/ (CH/ Me), 6.54/ 0.5, (Ar-H/ Ar-C, Ar-CH). 29 Si, { H} (75 MHz, C 6 D 6, 299 K): δ = ppm. DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.59/ 4.85 (Me/ CH), 6.54/ 7.09 (Ar-H/ Ar-H). 5

6 D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.59/ 4.85 (Me/ CH), 6.54/ 6.70, 6.89, 7.09 (Ar-H/ Ar-H, Ar-H, Ar-H). IR (KBr): ν/cm - = 2226 (ν (C N), s). Elemental analysis (%) C 25 H 33 N 5 Si 2 Zn (M = g/mol): calculated C 57.8, H 6.33, N 3.34; found C 57.23, H 6.0, N 3.2. Preparation of ZnL N(SiMe 3 ) 2 * B(C 6 F 5 ) 3, 3. eq of Tris(pentafluorophenyl)borane (7.6 mg in 2 ml of toluene, 34.2 mmol) was added to a toluene solution of (20 mg, 34.2 mmol). The reaction mixture was stirred for 0 min, filtered and dried several hours under vacuum. Compound 3 was isolated as bright yellow solid in 8 % yield. 6

7 H NMR (600 MHz, C 6 D 6, 299 K) 3 C {H} (00 MHz, C 6 D 6, 299 K) H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm = 0. (s, 9H, N(SiMe 3 ) 2 ), 0.25 (s, 9H, N(SiMe 3 ) 2 ),.03 (d, J =.4 Hz, 3H, CH(CH 3 ) 2 ),.5 (d, J =.4 Hz, 3H, CH(CH 3 ) 2 ),.25 (m, 6H, CH(CH 3 ) 2 ),.50 (s, 3H, Me),.63 (s, 3H, Me), 2.9 (s, H, CH(CH 3 ) 2 ), 2.99 (s, H, CH(CH 3 ) 2 ), 4.83 (s, H, CH), 6.50 (m, H, Ar-H d ), 6.85 (m, H, Ar-H), 6.95 (m, H, Ar-H), 7.05 (m, 2H, Ar-H), 7.0 (m, H, Ar-H), 7.38 (m, H, Ar-H e ). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = 4.6 (N(SiMe 3 ) 2 ), 5.47(N(SiMe 3 ) 2 ), (Me), (Me), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH), (Ar-C),

8 (C N), (Ar-CH), (Ar-CH), (Ar-CH d ), (Ar-CH), (Ar- CH), (Ar-CH e ), (Ar F5 -C), (Ar-CH), (Ar F5 -C), 40.3 (Ar F5 - C), 4.02 (Ar-C), 4.79 (Ar F5 -C), (Ar-C), (Ar-C), (Ar F5 -C), (Ar F5 -C), (Ar-C), (C=N), (C=N). GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) =.03/ 2.9, 2.99 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.5/ 2.9, 2.99 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.25/ 2.9, 2.99 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 2.9/.03,.5,.25 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 2.99/.03,.5,.25 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 4.83/.50,.63 (CH/ Me, Me), 6.50/ 6.85, 7.38 (Ar-H d / Ar-H, Ar-H e ), 6.85/ 6.95 (Ar-H/ Ar-H), 6.95/ 6.85 (Ar-H/ Ar-H), 7.05/ 7.0 (Ar-H/ Ar-H), 7.0/ 7.05 (Ar-H/ Ar-H), 7.38/ 6.50 (Ar- H e / Ar-H d ). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.25/ 4.6 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2 ), 0./ 5.47 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2 ),.03/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.5/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.25/ 24.70, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.50/ (Me/ Me),.63/ (Me/ Me), 2.9/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 2.99/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 4.83/ (CH/ CH), 6.50/ (Ar-CH d / Ar-CH d ), 6.85/ (Ar-CH/ Ar-CH), 6.95/ (Ar-CH/ Ar-CH), 7.05/ 24.49, (Ar-CH/ Ar- CH, Ar-CH ), 7.0/ (Ar-CH/ Ar-CH), 7.38/ (Ar-CH e / Ar-CH). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.25/ 4.6 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2 ), 0./ 5.47 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2 ),.03/ 24.53, 24.57, 28.52, 4.02 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C),.5/ 24.53, 28.52, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C),.25/ 24.70, 24.77, 28.52, 4.02, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C, Ar-C ),.50/ 97.73, (Me/ CH, C=N),.63/ 97.73, (Me/ CH, C=N), 2.9/ 24.70, 24.77, 24.49, 4.02, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH, Ar-C, Ar-C), 2.99/ 24.53, 24.57, 24.87, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH, Ar-C), 4.83/ 23.04, 24.23, 42.87, 54.83, 65.02, (CH/ Me, Me, Ar-C, Ar-C, C=N, C=N), 6.50/ 03.72, (Ar-CH d / Ar- C, Ar-CH), 6.85/ 03.72, (Ar-CH/ Ar-C, Ar-CH d ), 6.95/ 35.53, (Ar-CH/ Ar-CH e, Ar-C), 7.05/ 28.52, 28.72, 24.49, 24.87, 4.02, 42.35, (Ar-CH/ CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH, Ar-CH, Ar-C, Ar-C, Ar-C), 7.0/ 4.02 (Ar-CH/ Ar-C), 7.38/ 5.32, (Ar-CH e / C N, Ar-C). 8

9 DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) = 0./ 0.25,.25, 2.9, 2.99, 6.85 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH), 0.25/ 0.,.25, 2.9, 2.99, 6.85 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH),.03/.5,.25,.63, 2.9, 6.95 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH),.5/.03,.25,.63, 2.99, 6.95 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH),.63/ 2.9, 2.99, 6.95 (CH/ CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-H),.50/ 4.83 (Me/ CH),.63/ 0., 0.25, 4.83, (Me/ N(SiMe 3 ) 2, N(SiMe 3 ) 2, CH), 4.83/.50,.63 (CH/ Me, Me), 7.38/ 6.50 (Ar-H e / Ar-H d ). D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) = 0./ 0.25 (N(SiMe 3 ) 2 / N(SiMe 3 ) 2 ), 0.25/ 0. (N(SiMe 3 ) 2 / N(SiMe 3 ) 2 ),.03/.25, 2.9 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.5/.25, 2.99 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.25/.03,.5, 2.9, 2.99 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 2.9/.03,.25 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 2.99/.5,.25 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 4.83/.50,.63 (CH/ Me, Me), 6.50/ 6.85, 6.95, 7.38 (Ar-H d / Ar-H, Ar-H, Ar-H e ), 6.85/ 6.50, (Ar-H/ Ar-H d, Ar-H, Ar-H e ), 6.95/ 6.50, 6.85, 7.38 (Ar-H/ Ar-H d, Ar-H, Ar-H e ), 7.38/ 6.50, 6.85, 6.95 (Ar-H e / Ar-H d, Ar-H, Ar-H). 9 F NMR (564 MHz, C 6 D 6, 299 K): δ (m, 4F, m-c 6 F 5 ), (m, 2F, p-c 6 F 5 ), (m, 4F, o-c 6 F 5 ) ppm. B NMR (92 MHz, C 6 D 6, 299 K): δ ppm. IR (KBr): ν/cm - = 2305 (ν (C N), s). Elemental analysis (%) C 48 H 46 BF 5 N 4 Si 2 Zn (M = g/mol): calculated C H 4.23, N 5.; found C 52.60, H 4.33, N 5.0. Preparation of ZnL 2 N(SiMe 3 ) 2 * 2B(C 6 F 5 ) 3, 4. 2 eq of Tris(pentafluorophenyl)borane (39 mg in ml of toluene, 76.2 mmol) was added to a toluene solution of 2 (20 mg, 38 mmol). The reaction mixture was stirred for 0 min, filtered and dried several hours under vacuum. Compound 4 was isolated as bright yellow solid in 83 % yield. Single crystals for X-ray crystallography were grown by layering pentane onto a toluene solution of compound (4) at-30 o C. 9

10 H NMR (600 MHz, C 6 D 6, 299 K) 0

11 3 C {H} (00 MHz, C 6 D 6, 299 K) H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm = 0.33 (s, 8H, N(SiMe 3 ) 2 ),.50 (s, 6H, Me), 4.57 (s, H, CH ), 6.48 (m, 2H, Ar-H b ), 6.95 (m, 4H, Ar-H c,d ), 7.23 (m, 2H, Ar-H e ). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = 4.85 (N(Si(CH 3 ) 3 ) 2 ), (Me), 98.5 (CH), 4.48 (C N), 5.48 (Ar-C), (Ar-CH b ), (Ar-C), 28.5 (Ar-C), (Ar-CH e ), (Ar F5 -C), (Ar-CH), 38.7 (Ar F5 -C), (Ar F5 -C), 4.93 (Ar F5 -C), (Ar F5 -C), (Ar F5 -C), (Ar-C), (C=N). GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) =.50/ 4.57 (Me/ CH), 4.57/.50 (CH/ Me), 6.48/ 6.95, 7.23 (Ar-H b / Ar-H c,d, Ar-H e ), 6.95/ 6.48 (Ar-H c,d / Ar-H b ), 7.23/ 6.48, 6.95 (Ar-H e / Ar-H b, Ar-H c,d ). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.33/ 4.85 (N(Si(CH 3 ) 3 ) 2 / N(Si(CH 3 ) 3 ) 2 ),.50/ (Me/ Me), 4.85/ 98.5 (CH/ CH), 6.48/ (Ar-H b / Ar-CH b ), 6.95/ 27.87, (Ar-H c,d / Ar-CH, Ar-CH), 7.23/ (Ar-H e / Ar- CH e ). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 0.33/ 4.85 (N(Si(CH 3 ) 3 ) 2 / N(Si(CH 3 ) 3 ) 2 ),.50/ 98.5, (Me/ CH, C=N), 4.85/ 23.38, 53.88, (CH/ Me, Ar-C, C=N), 6.48/ (Ar-H b / Ar-CH), 6.95/ 35.28, (Ar-H c,d / Ar-CH e, Ar-C), 7.23/ 4.48, 38.63, (Ar-H e / C N, Ar-CH, Ar-C). DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) = 0.33/ 7.23 (N(SiMe 3 ) 2 / Ar-H e ),.50/ 4.57 (Me/ CH), 6.48/ 6.95, 7.23 (Ar-H b / Ar-H c,d, Ar-H e ), 6.95/ 6.48, 7.23 (Ar-H c,d / Ar- H b, Ar-H e ), 7.23/ 6.48, 6.95 (Ar-H e / Ar-H b, Ar-H c,d ). D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.50/ 4.57 (Me/ CH), 6.48/ 6.95, 7.23 (Ar-H b / Ar-H c,d, Ar-H e ), 6.95/ 6.48, 7.23 (Ar-H c,d / Ar-H b, Ar-H e ), 7.23/ 6.48, 6.95 (Ar- H e / Ar-H b, Ar-H c,d ). 9 F NMR (564 MHz, C 6 D 6, 299 K): δ (m, 4F, m-c 6 F 5 ), (m, 2F, p-c 6 F 5 ), (m, 4F, o-c 6 F 5 ) ppm. B NMR (92 MHz, C 6 D 6, 299 K): δ ppm. IR (KBr): ν/cm - = 230 (ν (C N), s). Elemental analysis (%) C 6 H 33 B 2 F 30 N 5 Si 2 Zn (M = g/mol): calculated C 47.30;, H 2.5, N 4.52; found C 47.4, H.65, N 4.8.

12 Preparation of ZnL C 6 F 5, 5. ZnL N(SiMe 3 ) 2 () (50 mg, 85.6 mmol) and HB(C 6 F 5 ) 2 (29.6 mg, 85.6 mmol) were dissolved in toluene and stirred at 80 o C for 2 h. The color of the solution was changed from yellow to orange. Evaporation of the solvent yielded pale orange, air-sensitive solid, that was washed several times with 2 ml cold pentane, and dried few hours under vacuum. Yield: 23.3 mg (39.4 mmol, 46 %). Single crystals for X-ray crystallography were grown by layering pentane onto a toluene solution of compound (5) at room temperature. H NMR (600 MHz, C 6 D 6, 299 K) 2

13 3 C {H} (00 MHz, C 6 D 6, 299 K) H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm =.4 (d, J =.5 Hz, 6H, CH(CH 3 ) 2 ),.23 (bs, 3H, CH(CH 3 ) 2 ),.36 (bs, 3H, CH(CH 3 ) 2 ),.72 (s, 3H, Me),.83 (s, 3H, Me), 3.3 (bs, 2H, CH(CH 3 ) 2 ), 3.45 (bs, 2H, CH(CH 3 ) 2 ), 5.02 (s, H, CH), 6.45 (t, H, Ar-H d ), 6.9 (t, H, Ar-H c ), 7.00 (d, H, Ar-H b ), 7.08 (m, 3H, Ar-H j,k ), 7.8 (d, H, Ar-H e ). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = 23.2 (Me), (Me), 23.8 (CH(CH 3 ) 2 ), 24.0 (CH(CH 3 ) 2 ), 24.3 (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), 96.7 (CH), 07.7 (Ar-C), 7.82 (C N), (Ar-CH j,k ), (Ar-CH d ), (Ar-CH b ), 27.0 (Ar-C), 28.9 (Ar-C), 33.6 (Ar-CH e ), (Ar- CH c ), (Ar F5 -C), (Ar F5 -C), (Ar F5 -C), 40.9 (Ar F5 -C), 4.68 (Ar-C), 42.4 (Ar-C), 44.0 (Ar-C), (Ar F5 -C), (Ar F5 -C), (Ar-C), (C=N), (C=N). GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) =.4/.23,.36 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 3.3/.4 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 3.45/.4 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 6.45/ 6.9, 7.8 (Ar-H d / Ar-H c, Ar-H e ), 6.9/ 6.45, 7.00, 7.8 (Ar-H c / Ar-H d, Ar-H b, Ar-H e ), 7.00/ 6.9 (Ar-H b / Ar-H c ), 7.8/ 6.45, 6.9 (Ar-H e / Ar-H d, Ar-H c ). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) =.4/ 23.2, 23.8 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ),.23/ 24.3 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.36/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.72/ (Me/ Me),.83/ 23.2 (Me/ Me), 3.3/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 3.45/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ), 5.02/ 96.7 (CH/ CH), 6.45/ 3

14 24.80 (Ar-H d / Ar-CH d ), 6.9/ (Ar-H c / Ar-CH c ), 7.00/ (Ar-H b / Ar-CH b ), 7.08/ (Ar-H j,k / Ar-CH j,k ), 7.8/ 33.6 (Ar-H e / Ar-CH e ). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) =.4/ 28.28, 28.40, 4.68, 42.4 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C, Ar-C),.72/ 96.7, (Me/ CH, C=N),.83/ 96.7, (Me/ CH, C=N), 5.02/ 23.2, 23.69, 65.00, (CH/ CH(CH 3 ) 2, CH(CH 3 ) 2, C=N, C=N), 6.45/ 07.7, 27.0 (Ar-H d / Ar-C, Ar-C), 6.9/ 33.6, (Ar-H c / Ar-CH e, Ar-C), 7.00/ 44.0 (Ar-H b / Ar-C), 7.8/ (Ar-H e / Ar-C). 9 F NMR (564 MHz, C 6 D 6, 299 K): δ (m, 2F, m-c 6 F 5 ), (m, F, p-c 6 F 5 ), (m, 2F, o-c 6 F 5 ) ppm. DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.4/.72 (CH(CH 3 ) 2 / Me),.72/.4, 5.02 (Me/ CH(CH 3 ) 2, CH ), 5.02/.72,.83 (CH/ Me, Me), 6.45/ 7.8 (Ar-H d / Ar-H e ), 6.9/ 7.00 (Ar-H c / Ar-H b ). D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.4/.23,.36, 3.3, 3.45 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 6.45/ 6.9, 7.00, 7.8 (Ar-H d / Ar-H c, Ar-H b, Ar-H e ), 6.9/ 6.45, 7.00, 7.8 (Ar-H c / Ar-H d, Ar-H b, Ar-H e ). IR (KBr): ν/cm - = 2249 (ν (C N), s). HRMS (ESI + H + ): m/z calculated (for (C 30 H 28 F 5 N 3 Zn)(C 24 H 30 N 3 )): Found:

15 Figure S. Experimental (above) and calculated (below) HRMS (ESI + H + ) spectra for (C 30 H 28 F 5 N 3 Zn)(C 24 H 30 N 3 ) Preparation of ZnL C 6 F 5 * B(C 6 F 5 ) 3, 6. eq of Tris(pentafluorophenyl)borane (33.8 mg in ml of toluene, 66 mmol) was added to a toluene solution of 5 (40 mg, 66 mmol). The reaction mixture was stirred for 20 min, filtered, washed with 3 ml cold pentane and dried under vacuum. Compound 6 was isolated as orange solid in 73 % yield. 5

16 H NMR (600 MHz, C 6 D 6, 299 K) 3 C {H} (00 MHz, C 6 D 6, 299 K) 6

17 H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm =.05 (d, J =.05 Hz, 3H, CH(CH 3 ) 2 ),.09 (d, J =.08 Hz, 3H, CH(CH 3 ) 2 ),.4 (d, J =.4 Hz, 3H, CH(CH 3 ) 2 ),.9 (d, J =.8 Hz, 3H, CH(CH 3 ) 2 ),.5 (s, 3H, Me),.63 (s, 3H, Me), 2.90 (s, H, CH(CH 3 ) 2 ), 5.00 (s, H, CH), 6.33 (t, H, Ar-H d ), 6.39 (d, H, Ar-H b ), 6.72 (t, H, Ar-H c ), 7.00 (m, 2H, Ar-H j,j ), 7.04 (m, H, Ar-H k ), 7.2 (d, H, Ar-H e ). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = (Me), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), 24. (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), (CH(CH 3 ) 2 ), 98.6 (CH), (Ar-C f ), 3.94 (C N), 24.7 (Ar-CH j ), (Ar-CH j ), (Ar- CH d ), (Ar-CH k ), (Ar-CH b ), (Ar-CH e ), 37.0 (Ar F5 -C), 37.7 (Ar- CH c ), (Ar F5 -C), (Ar F5 -C), (Ar-C i ), 4.84 (Ar-C i ), 4.89 (Ar F5 -C), 42.3 (Ar-C h ), (Ar F5 -C), (Ar F5 -C), (Ar-C a ), (C=N), (C=N). H- H GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) =.05/ 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.09/ 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.4/ 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.9/ 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.5/ 5.00 (Me/ CH), 2.90/.05,.09,.4,.9, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 5.00/.5,.63 (CH/ Me, Me), 6.33/ 6.72, 7.2 (Ar-H d / Ar-H c, Ar-H e ), 6.39/ 6.72, 7.2 (Ar-H b / Ar-H c, Ar-H e ), 6.72/ 6.33, 6.39, 7.2 (Ar-H c / Ar-H d, Ar-H b, Ar-H e ), 7.00/ 7.04 (Ar-H j,j / Ar-H k ), 7.04/ 7.00 (Ar- H k / Ar-H j,j ), 7.2/ 6.33 (Ar-H e / Ar-H d ). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) =.05/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.09/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.4/ (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.9/ 24. (CH(CH 3 ) 2 / CH(CH 3 ) 2 ),.5/ (Me/ CH 3 ),.63/ (Me/ CH 3 ), 2.90/ 28.67, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2 ), 5.00/ 98.6 (CH/ CH), 6.33/ (Ar-H d / Ar-CH d ), 6.39/ (Ar-H b / Ar-CH b ), 6.72/ 37.7 (Ar-H c / Ar-CH c ), 7.00/ 24.7, (Ar-H j,j / Ar-CH j, Ar-CH j ), 7.04/ (Ar-H k / Ar-CH k ), 7.2/ (Ar-H e / Ar-CH e ). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) =.05/ 23.60, 28.67, 28.78, 4.84 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C i ),.09/ 23.65, 28.67, 28.78, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C i ),.4/ 23.82, 28.67, 28.78, 4.84 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C i ),.9/ 24., 28.67, 28.78, (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-C i ),.5/ 98.6, 7

18 65.89 (Me/ CH, C=N),.63/ 98.6, (Me/ CH, C=N), 2.90/ 23.60, 23.65, 23.82, 24., 24.7, 24.78, 40.65, 4.84, 42.3 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH j, Ar-CH j, Ar-C i, Ar-C i, Ar-C h ), 5.00/ 23.58, 4.84, 42.3, 55.45, 65.89, (CH/ Me, Ar-C i, Ar-C h, Ar-C a, C=N, C=N), 6.33/ 03.95, (Ar-H d / Ar-C f, Ar-CH e ), 6.39/ (Ar-H b / Ar-C f ), 6.72/ 34.45, (Ar-H c / Ar-CH e, Ar-C a ), 7.00/ 28.67, 28.78, 24.7, 24.78, 4.84, 42.3 (Ar-H j,j / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-CH j, Ar-CH j, Ar-C i, Ar-C h ), 7.04/ (Ar-H k / Ar-C i ), 7.2/ 3.94, 37.7, (Ar-H e / C N, Ar-CH c, Ar-C a ). DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.05/.09,.9, 2.90, 7.00 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-H j,j ),.09/.05,.4, 2.90, 7.00 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-H j,j ),.4/.09, 2.90, 7.00 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-H j,j ),.9/.05, 2.90, 7.00 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, Ar-H j,j ),.5/ 2.90, 6.33 (Me/ CH(CH 3 ) 2, Ar-H j,j ),.63/.09,.4,.9 (Me/ CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 2.90/.05,.09,.4,.9,.63 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, Me), 5.00/.63 (CH/ Me), 6.33/ 6.39, 6.72, 7.2 (Ar-H d / Ar-H b, Ar- H c, Ar-H e ), 6.39/ 6.33, 6.72, 7.2 (Ar-H b / Ar-H d, Ar-H c, Ar-H e ), 6.72/ 6.33, 6.39, 7.2 (Ar- H c / Ar-H d, Ar-H b, Ar-H e ), 7.00/ 7.04 (Ar-H j,j / Ar-H k ), 7.04/ 7.00 (Ar-H k / Ar-H j,j ), 7.2/ 6.33, 6.39, 6.72 (Ar-H e / Ar-H d, Ar-H b, Ar-H c ). D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.05/.09,.4,.9, 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ),.09/.05,.4,.9, 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ),.4/.05,.4,.9, 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ),.9/.05,.4,.9, 2.90 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 2.90/.05,.09,.4,.9 (CH(CH 3 ) 2 / CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2, CH(CH 3 ) 2 ), 5.00/.5,.63 (CH/ Me, Me), 6.33/ 6.72 (Ar-H d / Ar-H c ), 6.39/ 6.33 (Ar-H b / Ar-H d ), 6.72/ 6.33, 6.39 (Ar-H c / Ar-H d, Ar- H b ), 7.00/ 7.04 (Ar-H j,j / Ar-H k ), 7.04/ 7.00 (Ar-H k / Ar-H j,j ), 7.2/ 6.33 (Ar-H e / Ar-H c ). 9 F NMR (564 MHz, C 6 D 6, 299 K): δ (m, 6F, m-c 6 F 5 ), (m, 2F, m-c 6 F 5 ), (m, 3F, p-c 6 F 5 ), (m, F, p-c 6 F 5 ), (m, 6F, o-c 6 F 5 ), (m, 2F, o-c 6 F 5 ) ppm. 9 F- 9 F GCOSY (564 MHz / 564 MHz, C 6 D 6, 299 K): δ ( 9 F)/ δ ( 9 F) = / , (m-c 6 F 5 / p-c 6 F 5, o-c 6 F 5 ), / -53.9, (m-c 6 F 5 / p-c 6 F 5, o-c 6 F 5 ), - 8

19 55.54/ , (p-c 6 F 5 / m-c 6 F 5, o-c 6 F 5 ), -53.9/ , (p-c 6 F 5 / m- C 6 F 5, o-c 6 F 5 ), / , (o-c 6 F 5 / m-c 6 F 5, p-c 6 F 5 ), -6.72/ , (o-c 6 F 5 / m-c 6 F 5, p-c 6 F 5 ) ppm. B NMR (92 MHz, C 6 D 6, 299 K): δ ppm. IR (KBr): ν/cm - = 239 (ν (C N), s). Elemental analysis (%) C 48 H 28 BF 20 N 3 Zn * 0.5 C 5 H 2 : calculated C H 3.0, N 3.69; found C 53.44, H 2.75, N Preparation of ZnL 2, 7. Diketimine L 2 H (40 mg, 33.2 mmol) and Zn{N(SiMe 3 ) 2 } 2 (34.2 mg, 88.8 mmol) were reacted in toluene (5 ml) for 2 hours at 80 o C. The residue obtained after evaporation of the solvent was washed with pentane and dried under vacuum to yield yellow powder of 7 (36.5 mg, 62 %). Single crystals for X-ray crystallography were grown by layering pentane onto a toluene solution of compound (7) at-30 o C. 9

20 H NMR (600 MHz, C 6 D 6, 299 K) 3 C {H} (00 MHz, C 6 D 6, 299 K) H NMR (600 MHz, C 6 D 6, 299 K): δ/ppm =.54 (s, 6H, Me),.55 (s, 3H, Me),.57 (s, 6H, Me),.68 (s, 8H, Me),.69 (s, 6H, Me),.82 (s, 3H, Me),.98 (s, 6H, Me), 4.58 (s, H, CH), 4.63 (s, 3H, CH), 4.65 (s, 2H, CH), 4.67 (s, 2H, CH), 6.5 (m, 2H, Ar-H), 6.53 (m, 3H, Ar-H), 6.54 (m, 3H, Ar-H), 6.55 (m, H, Ar-H), 6.56 (m, 4H, Ar-H), 6.58 (m, 2H, Ar-H), 6.59 (m, H, Ar-H), 6.63 (m, H, Ar-H), 6.64 (m, H, Ar-H), 6.7 (m, H, Ar-H), 6.72 (m, H, Ar-H), 6.75 (m, H, Ar-H), 6.76 (m, H, Ar-H), 6.78 (m, H, Ar-H), 6.79 (m, 20

21 H, Ar-H), 6.88 (m, H, Ar-H), 6.90 (m, H, Ar-H), 6.9 (m, H, Ar-H), 6.92 (m, H, Ar- H), 6.95 (m, H, Ar-H), 6.96 (m, 3H, Ar-H), 6.98 (m, 2H, Ar-H), 7.02 (m, 2H, Ar-H), 7.07 (m, 5H, Ar-H), 7.09 (m, 5H, Ar-H), 7.0 (m, H, Ar-H), 7. (m, H, Ar-H), 7.3 (m, 2H, Ar-H), 7.5 (m, 2H, Ar-H), 7.7 (m, 2H, Ar-H), 7.8 (m, H, Ar-H), 7.9 (m, H, Ar-H), 7.2 (m, H, Ar-H), 7.22 (m, H, Ar-H), 7.29 (m, 2H, Ar-H), 7.37 (m, H, Ar-H), 7.45 (m, H, Ar-H), 7.9 (m, 2H, Ar-H). 3 C { H} NMR (00 MHz, C 6 D 6, 299 K): δ/ppm = (Me), 22.7 (Me), 23.2 (Me), (Me), (Me), (CH), (CH), (CH), (CH), (Ar-C), (Ar-C), (Ar-C), 09.3 (Ar-C), 09.9 (Ar-C), 6.48 (C N), 7.08 (C N), 7.6 (C N), 7.72 (C N), 8.00 (C N), 8.20 (C N), (Ar), (Ar-CH), 23.6 (Ar), (Ar-CH), 24.8 (Ar), (Ar), (Ar), (Ar- CH), (Ar), 25.5 (Ar), 26. (Ar), (Ar-CH), (Ar), 27.2 (Ar), 32.7 (Ar-CH), (Ar), (Ar), (Ar), (Ar), (Ar), 33.0 (Ar), (Ar), 33.4 (Ar-CH), (Ar-CH), (Ar), (Ar), (Ar- CH), 35.2 (Ar), 5.62 (Ar), (Ar), (Ar), (Ar), (Ar), (Ar), (C=N), (C=N), (C=N), (C=N), (C=N), 69.7 (C=N), (C=N). GCOSY (600 MHz / 600 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( H) = 6.5/ 6.95, 6.96, 6.98, 7.07, 7.09 (Ar-H/ Ar-H, Ar-H, Ar-H, Ar-H), 6.55/ 6.78, 6.79 (Ar-H/ Ar-H, Ar-H), 6.56/ 6.7, 6.72 (Ar-H/ Ar-H, Ar-H), 6.58/ 7.8 (Ar-H/ Ar-H), 6.59/ 7.8 (Ar-H/ Ar-H), 6.63/ 7.22 (Ar-H/ Ar-H), 6.64/ 7.22 (Ar-H/ Ar-H), 6.7/ 6.53, 6.55, 6.56 (Ar-H/ Ar-H, Ar-H, Ar-H), 6.78/ 6.54, 6.58 (Ar-H/ Ar-H, Ar-H), 6.90/ 6.5, 6.54 (Ar-H/ Ar-H, Ar-H), 6.95/ 6.5, 6.54, 7.07, 7.09 (Ar-H/ Ar-H, Ar-H, Ar-H, Ar-H), 6.98/ 6.5, 6.54, 7.07, 7.09 (Ar-H/ Ar-H, Ar- H, Ar-H, Ar-H), 7.07/ 6.5, 6.54, 6.95, 6.98 (Ar-H/ Ar-H, Ar-H, Ar-H, Ar-H), 7.09/ 6.5, 6.54, 6.95, 6.98 (Ar-H/ Ar-H, Ar-H, Ar-H, Ar-H), 7.3/ 7.45 (Ar-H/ Ar-H), 7.7/ 6.56 (Ar- H/ Ar-H), 7.8/ 6.59, 7.9 (Ar-H/ Ar-H, Ar-H), 7.9/ 6.54 (Ar-H/ Ar-H), 7.22/ 6.54, 6.58, 6.63, 6.64 (Ar-H/ Ar-H, Ar-H, Ar-H, Ar-H), 7.45/ 7.3 (Ar-H/ Ar-H), 7.9/ 7.5, 7.8 (Ar- H/ Ar-H, Ar-H). 3 C-GHSQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) =.68/ 23.2 (Me/ Me),.68/ (Me/ Me),.68/ (Me/ Me), 4.63/ (CH/ CH), 4.65/ (CH/ CH), 4.67/ (CH/ CH), 6.5/ 23.48, (Ar-H/ Ar-CH, Ar-CH), 6.53/ (Ar-H/ 2

22 Ar-CH), 6.58/ (Ar-H/ Ar-CH), 6.95/ (Ar-H/ Ar-CH), 6.96/ 33.4, (Ar-H/ Ar-CH, Ar-CH), 7.07/ 32.7, (Ar-H/ Ar-CH, Ar-CH). H, 3 C-GHMQC (600 MHz / 00 MHz, C 6 D 6, 299 K): δ ( H)/ δ ( 3 C) = 4.63/ 22.66, 22.7, (CH/ Me, Me, CH), 7.7/ (Ar-H/ CH). DPFGNOE (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.54/.55,.57 (Me/ Me, Me),.55/.54,.57 (Me/ Me, Me),.57/.54,.55 (Me/ Me, Me),.68/.69, 4.63 (Me/ Me, Me),.69/.68, 4.63 (Me/ Me, CH), 4.63/.68, 4.65, 4.67 (CH/ Me, CH, CH), 4.65/.68, 4.63, 4.67 (CH/ Me, CH, CH), 4.67/.68, 4.63, 4.65 (CH/ Me, CH, CH). D TOCSY (600 MHz, C 6 D 6, 299 K): δ ( H ir ) / δ ( H res ) =.54/.55,.57 (Me/ Me, Me),.55/.54,.57 (Me/ Me, Me),.57/.54,.55 (Me/ Me, Me),.68/.69 (Me/ Me),.69/.68 (Me/ Me), 4.63/ 4.65, 4.67 (CH/ CH, CH), 4.65/ 4.63, 4.67 (CH/ CH, CH), 4.67/ 4.63, 4.65 (CH/ CH, CH). IR (KBr): ν/cm - = 2226 (ν (C N), s). Elemental analysis (%) (M = g/mol): calculated C 68.73, H 4.55, N 6.87; found C 68.42, H 4.25, N Zn 2 (L ) 2 (OH) 2 ( a ) Zn 2 (L ) 2 (OH) 2 ( a ). Zinc amide complex with a long stay in a toluene solution was spotted to decompose to bimetallic zinc complex Zn 2 (L ) 2 (OH) 2 ( a ), single crystals of this compound suitable for X-ray diffraction were obtained, but only in quantities insufficient for further characterization. Scheme S. Synthesis of Zn 2 (L ) 2 (OH) 2 ( a ) a crystallizes in the triclinic space group Pī as a hydroxide-bridged centrosymmetric dimer (Scheme S, Figure S2). The Zn-O bond lengths are almost identical (Zn-O.969(); 22

23 Zn-O*.966() Ȧ) as was previously observed for [MesnacnacZn(µ-OH)] 2, whereas terminal OH groups show shorter Zn-O bond lengths ( Ȧ). The Zn 2 O 2 metallacycle in a is planar (dihedral angle Zn-O-Zn*-O* is -0.0() o ) with the Zn Zn distance 3.002() Ȧ, while in [MesnacnacZn(µ-OH)] 2 the distance between two atoms of zinc is Ȧ. Zn-N bond lengths within the complex a are slightly larger compared to the starting amide zinc complex (Figure, Figure S2). Four-coordinate zinc a adopts distorted tetrahedral geometry (O-Zn-N 5.5() o, O*-Zn-N2 2.() o, N-Zn-N2 97.2() o ). Figure S2. X-ray crystal structure of a with thermal ellipsoids drawn at the 50 % probability level. The hydrogen atoms are omitted for clarity. Selected bond lengths (Ȧ) and angles (deg): Zn-O.969(), Zn-O*.966(), Zn-Zn* 3.002(), Zn-N.997(2), Zn-N2.989(2), O-O* 2.544(), O-Zn-O* 80.6(), N-Zn-N2 97.2(), O-Zn-N 5.5(), O*-Zn-N2 2.(), Zn-O-Zn*-O* -0.0(). 3. Crystallography Characterization. X-Ray diffraction: Data sets were collected with a Nonius KappaCCD diffractometer. Programs used: data collection, COLLECT (R. W. W. Hooft, Bruker AXS, 2008, Delft, The Netherlands); data reduction Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 997, 276, ); absorption correction, Denzo (Z. Otwinowski, D. Borek, W. Majewski, W. Minor, Acta Crystallogr. 2003, A59, ); structure solution SHELXS- 23

24 97 (G. M. Sheldrick, Acta Crystallogr. 990, A46, ); structure refinement SHELXL-97 (G. M. Sheldrick, Acta Crystallogr. 2008, A64, 2-22) and graphics, XP (BrukerAXS, 2000). R-values are given for observed reflections, and wr 2 values are given for all reflections. The crystal data and refinement of, a, 2, 4, 5 and 7 are summarized below. X-ray crystal structure analysis of (erk7483): formula C 30 H 46 N 4 Si 2 Zn, M = , pale yellow crystal, 0.4 x 0. x 0.03 mm, a = (), b = (2), c = 9.825(3) Å, α = 7.047(), β = 8.865(), γ = (), V = () Å 3, ρ calc =.93 gcm -3, µ = mm -, empirical absorption correction (0.890 T 0.974), Z = 4, triclinic, space group P- (No. 2), λ = Å, T = 223(2) K, ω and φ scans, 2985 reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.62 Å -, 367 independent (R int = 0.047) and 0493 observed reflections [I>2σ(I)], 69 refined parameters, R = 0.05, wr2 = 0.22, max. (min.) residual electron density 0.53 (-0.42) e.å -3, the hydrogens were calculated and refined as riding atoms. X-ray crystal structure analysis of 2 (erk7466): formula C 50 H 66 N 0 Si 4 Zn 2, M = , colorless crystal, 0.23 x 0.2 x 0.5 mm, a = (3), b =.20(4), c = (6) Å, α = (), β = (2), γ = 7.743(2), V = 635.4() Å 3, ρ calc =.066 gcm -3, µ = mm -, empirical absorption correction (0.829 T 0.884), Z =, triclinic, space group P- (No. 2), λ = Å, T = 223(2) K, ω and φ scans, 2752 reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.62 Å -, 6468 independent (R int = 0.042) and 5746 observed reflections [I>2σ(I)], 306 refined parameters, R = 0.057, wr2 = 0.36, max. (min.) residual electron density 0.46 (-0.47) e.å -3, the hydrogens were calculated and refined as riding atoms. X-ray crystal structure analysis of 4 (erk7454): formula C 6 H 33 B 2 F 30 N 5 Si 2 Zn, M = , pale yellow, 0.40 x 0.30 x 0.5 mm, a = (3), b = (3), c = 5.96(3) Å, β = (), V = (2) Å 3, ρ calc =.599 gcm -3, µ = 0.55 mm -, empirical absorption correction (0.809 T 0.922), Z = 4, monoclinic, space group C2/c (No. 5), λ = Å, T = 273(2) K, ω and φ scans, 2499 reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.59 Å -, 5538 independent (R int = 0.050) and 4537 observed reflections 24

25 [I>2σ(I)], 495 refined parameters, R = 0.06, wr2 = 0.64, max. (min.) residual electron density 0.35 (-0.25) e.å -3, the hydrogens were calculated and refined as riding atoms. X-ray crystal structure analysis of 5 (erk752): formula C 60 H 56 N 6 F 0 Zn 2, M = 8.85, pale yellow crystal, 0.8 x 0.08 x 0.06 mm, a = (), b = (3), c = (3) Å, β = 9.327(), V = 5639.() Å 3, ρ calc =.392 gcm -3, µ = mm -, empirical absorption correction (0.850 T 0.946), Z = 4, monoclinic, space group P2 /c (No. 4), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.62 Å -, 342 independent (R int = 0.054) and 8289 observed reflections [I>2σ(I)], 75 refined parameters, R = 0.057, wr2 = 0.20, max. (min.) residual electron density 0.37 (-0.42) e.å -3, the hydrogens were calculated and refined as riding atoms. X-ray crystal structure analysis of 7 (erk75): formula C 38 H 30 N 8 Zn, M = , yellow crystal, 0.6 x 0.07 x 0.03 mm, a = (3), b =.355(4), c = (6) Å, α = 72.96(), β = 83.43(2), γ = (2), V = 680.4() Å 3, ρ calc =.32 gcm -3, µ = mm -, empirical absorption correction (0.886 T 0.977), Z = 2, triclinic, space group P- (No. 2), λ = Å, T = 223(2) K, ω and φ scans, 4852 reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.59 Å -, 575 independent (R int = 0.045) and 525 observed reflections [I>2σ(I)], 428 refined parameters, R = 0.049, wr2 = 0.2, max. (min.) residual electron density 0.62 (-0.36) e.å -3, the hydrogens were calculated and refined as riding atoms. X-ray crystal structure analysis of a (erk7487): formula C 48 H 58 N 6 O 2 Zn 2, M = 88.74, pale yellow crystal, 0.5 x 0.2 x 0.07 mm, a = (3), b = 0.226(4), c = (4) Å, α = 0.950(2), β = (2), γ = 04.72(), V = 5.6(7) Å 3, ρ calc =.32 gcm -3, µ =.20 mm -, empirical absorption correction (0.850 T 0.925), Z =, triclinic, space group P- (No. 2), λ = Å, T = 223(2) K, ω and φ scans, 440 reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.62 Å -, 4478 independent (R int = 0.037) and 4207 observed reflections [I>2σ(I)], 27 refined parameters, R = 0.032, wr2 = 0.085, max. (min.) residual electron density 0.23 (-0.38) e.å -3, the hydrogen at O atom was refined freely, but with O- H distance restraints (DFIX and fixed U-value); others were calculated and refined as riding atoms. 25

26 4. H NMR spectra of PLLA formation. Figure S7. H NMR spectra of PLLA formation in C 6 D 6 CD 3 ([LA]/[] = 250) 26

27 5. H NMR spectra of partially dissociated complex 2. Figure S8. H NMR spectra of partially dissotiated complex 2 (see signals of compound 2 and signals of compound 7). 6. H NMR spectrum of PLLA 27

28 Figure S9. H NMR spectrum (200 MHz, CDCl 3 ) of the oligomer product obtained from a reaction between L-LA and at room temperature. 7. MALDI-TOF spectrum of PLLA Figure S0. MALDI-TOF spectrum of the oligomer product obtained from a reaction between L-LA and at room temperature. 8. PLLA SEC characterization Figure S. GPC traces of polymer produced using at 25 o C. See Entry, Table 2 (manuscript). 28

29 References (a) S. Schulz, J. Spielmann, D. Blaser and C. Wolper, Chem. Commun., 20, 47, ; (b) S. S. Al-Juaid, N. H. Buttrus, C. Eaborn, P. B. Hitchcock, A. T. L. Roberts, J. D. Smith and A. C. Sullivan, Chem. Commun., 986, 908. (c) G. Anantharaman and K. Elango, Organometallics, 2007, 26,