[MnBrL(CO) 4 ] (L = Amidinatogermylene): Reductive Dimerization, Carbonyl Substitution, and Hydrolysis Reactions

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1 SUPPORTING INFORMATION (Organometallics, Ms. ID: om w) [MnBrL(CO) 4 ] (L = Amidinatogermylene): Reductive Dimerization, Carbonyl Substitution, and Hydrolysis Reactions Javier A. Cabeza,* Pablo García-Álvarez,* Roberto Gobetto, Laura González-Álvarez, Carlo Nervi, Enrique Pérez-Carreño, and Diego Polo Departamento de Química Orgánica e Inorgánica-IUQOEM, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Oviedo-CSIC, E Oviedo, Spain Dipartimento di Chimica, Università di Torino, via P. Giuria 7, Torino, Italy Departamento de Química Física y Analítica, Universidad de Oviedo, E Oviedo, Spain S1

2 C 6 HD 5 CHs (Ph) tol. C 6 D 6 Ph COs NCN C ( t Bu) Figure S1. 1 H (top) and 13 C{ 1 H} (bottom) NMR spectra of [Mn 2 {Ge( i Pr 2 bzam) t Bu} 2 (CO) 8 ] (5) in C 6 D 6 (20 ºC). S2

3 C 6 HD 5 CHs (Ph) tol. C 6 D 6 Ph COs NCN C ( t Bu) Figure S2. 1 H (top) and 13 C{ 1 H} (bottom) NMR spectra of [Mn 2 {Ge( i Pr 2 bzam) t Bu}(CO) 9 ] (6) in C 6 D 6 (20 ºC). S3

4 C 6 HD 5 CHs (Ph) C 6 D 6 Ph COs NCN C ( t Bu) Figure S3. 1 H (top) and 13 C{ 1 H} (bottom) NMR spectra of trans-mer- [MnBr{Ge( i Pr 2 bzam) t Bu} 2 (CO) 3 ] (7) in C 6 D 6 (20 ºC). S4

5 PMe 3 C 6 HD 5 CHs (Ph) C 6 D 6 Ph PMe 3 COs NCN C ( t Bu) Figure S4. 1 H (top) and 13 C{ 1 H} (bottom) NMR spectra of trans-mer- [MnBr{Ge( i Pr 2 bzam) t Bu}(PMe 3 )(CO) 3 ] (8) in C 6 D 6 (20 ºC). S5

6 CH 3 (CN t Bu) CHs (Ph) C 6 HD 5 C 6 D 6 CH 3 (CN t Bu) Ph C ( t Bu) COs NCN CN t Bu C (CN t Bu) Figure S5. 1 H (top) and 13 C{ 1 H} (bottom) NMR spectra of fac- [MnBr{Ge( i Pr 2 bzam) t Bu}(CN t Bu)(CO) 3 ] (9) in C 6 D 6 (20 ºC). S6

7 + CHs (Ph) CHDCl 2 CD 2 Cl 2 COs NCN Ph C ( t Bu) Figure S6. 1 H (top) and 13 C{ 1 H} (bottom) NMR spectra of [ i Pr 2 bzamh 2 ][MnBr{Ge(OH) 2 t Bu}(CO) 4 ] (10) in CD 2 Cl 2 (20 ºC). S7

8 Figure S7. Comparative IR spectra (in toluene solution, ν CO and ν CN absorptions) of compounds 7, 8, and 9, showing the different ν CO patterns of the mer- (7,8) and fac-arrangements (9) of their CO ligands (the band of 9 at cm 1 is due to its CN t Bu ligand). S8

9 Figure S8. HOMO (left) and LUMO (right) of complex 1 shown at an isosurface value of ± 0.05 (adapted from: Cabeza, J. A.; García-Álvarez, P.; Pérez-Carreño, E.; Polo, D. Inorg. Chem. 2014, 53, ) Current (µa) CO 2 + 5% H 2 O Ar + 5% H 2 O Potential (V) vs. Fc/Fc + Figure S9. CV of a 2 mm solution of 1 in acetonitrile at 0.2 V/s under Ar + 5% of H 2 O (blue) and under CO 2 + 5% of H 2 O (red). S9

10 Figure S10. Chronoamperometric data of complex 1 during exhaustive electrolysis at 2.3 V vs. Fc/Fc + MeCN solution with 5% of water. in a 2000 H2 CO ppm Time (min) Figure S11. CO (red) and H 2 (black) evolution during the first 140 min of electrolysis at 2.3 V vs. Fc/Fc + of 2 mm MeCN/H 2 O (5%) solutions of 1. The gas was automatically sampled every 3.4 min and was analyzed by gas chromatography. S10

11 Insights into the electrocatalytic behavior of complex 10 were obtained performing exhaustive electrolysis under a constant flow of CO 2 (8.67 ml min 1 ) and monitoring the amount of H 2 and CO production by gas chromatography. The applied reduction potential, 2.3 V vs. Fc/Fc +, is slightly more negative than that of the first reduction process. Under these experimental conditions, during the first 23 min (Figures S12 and S13), a little of hydrogen was produced. In the first 23 min, the concentration of H 2 produced was 14 ppm, while the concentration of CO was 368 ppm. This probably indicates that traces of hydrogen could be produced by the reduction of 10. At the 23 th min, 5% of water was added to the solution and the current abruptly increased. As expected, H 2 was significantly produced, but the concentration of the produced CO did not vary. At the end of the recorded time (103 min), the total TONs of the H 2 and CO produced were 1.8 and 0.8, respectively H2 CO ppm Time (min) Figure S12. CO (red) and H 2 (black) evolution during the first 103 min of electrolysis at 2.3 V vs. Fc/Fc + of 2 mm MeCN solution of 10. Water (5%) was added after 23 min. The gas was automatically sampled every 3.4 min and was analyzed by gas chromatography. Figure S13. Chronoamperometric data during the exhaustive electrolysis at 2.3 V vs. Fc/Fc + of a MeCN solution of 10. Addition of water (23 th minute) significantly increased the recorded current. S11

12 Table S1. Crystal, Measurement, and Refinement Data for the Compounds Studied by X-Ray Diffraction formula C 42 H 56 Ge 2 Mn 2 N 4 O 8 C 26 H 28 GeMn 2 N 2 O 9 0.5(C 37 H 56 BrGe 2 MnN 4 O 3 ) C 25 H 37 BrGeMnN 3 O 3 2(C 21 H 32 BrGeMnN 2 O 6 ) fw cryst syst monoclinic monoclinic monoclinic monoclinic triclinic space group P2 1 /n P21/c P21/c Cc P 1 a, Å (5), (4) (2) 9.456(2) (4) b, Å (4) (3) (3) (4) (5) c, Å (3) (4) (2) (4) (5) α, deg (3) β, deg (2) (2) (2) (3) (3) γ, deg (4) V, Å (2) (1) (7) 2897(1) (1) Z F(000) D calcd, g cm µ, mm (Cu Kα) (Cu Kα) (Cu Kα) (Mo Kα) (Cu Kα) cryst size, mm 0.23 x 0.09 x x 0.06 x x 0.09 x x 0.18 x x 0.22 x 0.15 T, K 152(2) 123(2) 123(2) 100(2) 123(2) θ range, deg 3.66 to to to to to min./max. h, k, l 19/18, 19/13, 21/21 17/13, 14/13, 18/21 12/9, 15/20, 14/14 12/12, 0/21, 24/24 10/13, 16/15, 24/23 no. collected reflns no. unique reflns no. reflns with I> 2σ(I) no. params/restraints 537/0 368/0 239/0 321/6 623/0 GOF (on F 2 ) R 1 (on F, I > 2σ(I)) wr 2 (on F 2, all data) min./max. Δρ, e Å / / / / /0.376 CCDC dep. no S12