Supporting Information

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1 Supporting Information Jacques et al /pnas SI Text Crystal Structure Analysis. Crystallographic data are summarized in Table S2. Data collection was performed at 150 K with an Oxford-diffraction XCalibur S diffractometer with a CCD area detector with graphite monochromated Mo-K radiation ( Å). Empirical absorption correction (Abspack) was performed. Molecular structures were solved by direct methods and refined on F 2 by full-matrix least-squares techniques with the SHELXTL package with anisotropic thermal parameters. All nonhydrogen atoms were refined anisotropically; hydrogen atoms were found by Fourier synthesis and refined with individual isotropic displacement parameters. X-ray suitable crystals of the complexes [Ni(DO)(DOH)pn]- (ClO 4 ) and [Co(DO)(DOH)pnBr 2 ] were grown by vapor diffusion of diethyl ether into a filtered concentrated solution of each complex in acetone. Crystals of [Co(MO)(MOH)pnCl 2 ] were grown by vapor diffusion of diethyl ether into a filtered concentrated solution in DMSO. The atomic coordinates have been deposited in the Cambridge Structural Database, Cambridge Crystallographic Data Centre (CSD reference nos for compound [Co(MO)(MO- H)pnCl 2 ], for [Ni(DO)(DOH)pn] (ClO 4 ), and for [Co(DO)(DOH)pnBr 2 ]). Evaluation of Thermodynamic Equilibrium Constants for Homolytic and Heterolytic Hydrogen Evolution. The equilibrium constants for homolytic and heterolytic H 2 evolution from p-cyanoanilium tetrafluoroborate in CH 3 CN can be determined using the methodology developed by Kellett and Spiro (1), based on the known values of standard potentials of the following couples: p- cyanoanilinium tetrafluoroborate/h 2 (E 0.59 V vs. Ag/ AgCl), Co II /Co I and Co III /Co II for the different complexes. Both pathways are considered as the sum of one reaction and one or two redox half-equations. Heterolytic route: 1/2 Co I AH 1/2 Co III 1/2H 2 A [1] 1/2 Co III e 1/2 Co II 1/2 Co II e 1/2 Co I Net reaction: AH e 1/2H 2 A Thus, r G 1 1/2 E Co III /Co II 1/2 E Co II /Co I E H /H 2 Homolytic route: Co I AH CoI II 1/2H 2 A [2] Co II e Co I Net reaction: AH e 1/2H 2 A Thus, r G E Co II /Co I E H /H 2 Table S1 contains the calculated values for the thermodynamic equilibrium constants for homolytic and heterolytic hydrogen evolution catalyzed by [Co(DO) 2 BF 2 pnbr 2 ], [Co(DO)(DOH)pnBr 2 ], and [Co(dmgBF 2 ) 2 (CH 3 CN) 2 ]. 1. Kellett RM, Spiro TG (1985) Cobalt(I) porphyrin catalysis of hydrogen-production from water. Inorg Chem 24: of14

2 Fig. S1. X-ray structure of [Co(DO)(DOH)pnBr 2 ] (50% thermal ellipsoids). 2of14

3 Fig. S2. X-ray structure of the cation in [Ni(DO)(DOH)pn] (ClO 4 ) (50% thermal ellipsoids). 3of14

4 Fig. S3. Cyclic voltammograms of [Co((DO) 2 BF 2 )pnbr 2 ] (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of tosic acid monohydrate (0, 1, 3, 5, 10 equiv.) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 4of14

5 Fig. S4. Cyclic voltammograms of [Co((DO) 2 BF 2 )pnbr 2 ] (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of anilinium tetrafluoroborate (0, 1, 3, 5, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 5of14

6 Fig. S5. Cyclic voltammograms of [Co((DO) 2 BF 2 )pnbr 2 ] (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of trifluoroacetic acid (0, 3, 5, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 6of14

7 Fig. S6. Cyclic voltammograms of [Co(DO)(DOH)pnBr 2 ] (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N] [BF 4 ] in presence of tosic acid monohydrate (0, 1, 3, 5, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 7of14

8 Fig. S7. Cyclic voltammograms of [Co(DO)(DOH)pnBr 2 ] (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of trifluoroacetic acid (0, 1, 3, 5, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 8of14

9 Fig. S8. Cyclic voltammograms of [Ni(DO)(DOH)pn](ClO 4 ) (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of triethylammonium hydrochloride (0, 3, 5, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 9of14

10 Fig. S9. Cyclic voltammograms of [Ni(DO)(DOH)pn] (ClO 4 ) (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of anilinium tetrafluoroborate (0, 1, 3, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 10 of 14

11 Fig. S10. Cyclic voltammograms of [Ni(DO) 2 (BF 2 )pn](cio 4 ) (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of tosic acid monohydrate (0, 1, 3, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 11 of 14

12 Fig. S11. Cyclic voltammograms of [Ni(MO)(MOH)pnCl] (1 mm) in CH 3 CN solution containing 0.1 M [ n Bu 4 N][BF 4 ] in presence of p-cyanoanilinium tetrafluoroborate (0, 3, 5, 10 equiv) recorded at a glassy carbon electrode (scan rate 100 mv s 1 ). 12 of 14

13 Table S1. Calculated values for the thermodynamic equilibrium constants for homolytic and heterolytic hydrogen evolution catalyzed by [Co(DO)(DOH)pnBr 2 ], [Co((DO) 2 BF 2 )pnbr 2 ], and [Co(dmgBF 2 ) 2 (CH 3 CN) 2 ] E 1/2 (M III /M II ) E 1/2 (M II /M I ) r G (1) r G (2) heterolytic, kj mol 1 homolytic, kj mol 1 [Co(DO)(DOH)pnBr 2 ] [Co((DO) 2 BF 2 )pnbr 2 ] [Co(dmgBF 2 ) 2 (CH 3 CN) 2 ] 0.2 (irrev. cathodic) of 14

14 Table S2. Crystal data and structural refinement details for complexes Co(MO)(MOH)pnCl 2, Ni(DO)(DOH)pn (ClO 4 ), and Co(DO)(DOH)pnBr 2 Compound Co(MO)(MOH)pnCl 2 Ni(DO)(DOH)pn (ClO 4 ) Co(DO)(DOH)pnBr 2 Formula C 9 H 15 Cl 2 CoN 4 O 2 C 11 H 19 ClN 4 NiO 6 C 11 H 19 Br 2 CoN 4 O 2 Molecular mass, Da Color Green Yellow Green Crystal size mm mm mm Crystal system Monoclinic Monoclinic Monoclinic Space group Pbca P2 1 /c P2 1 /n a, Å (4) (10) (4) b, Å (4) (3) (3) c, Å (6) (2) (3), , (17) (2), V, Å (16) (4) (13) Z calcd, mg m ,cm Reflections collected 9,562 15,877 18,811 Unique reflections (R int ) 3,073 (R int ) 3,757 (R int ) 7,259 (R int ) Observed reflections I 2 (I) 1,789 2,869 4,374 Refined parameters R indices, all data R , wr R , wr R , wr Final R indices, observed reflections R , wr R , wr R , wr Goodness of fit S (max/min), e Å and and and R1 F o F c / F o. wr2 { w(f o 2 F c 2 ) 2 / w(f o 2 ) 2 } 1/2. w 1/ 2 (F o 2 ) (ap) 2 bp, where P 2F c 2 Max(F o 2,0) /3 (see CIF for a and b values). 14 of 14