Electronic Supplementary Information

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1 Electronic Supplementary Information Dynamics of H-atom exchange in stable cis-dihydrogen/hydride complexes of ruthenium(ii) bearing phosphine and N N bidentate ligands Barun Bera, Yogesh P. Patil, Munirathinam Nethaji and Balaji R. Jagirdar* Department of Inorganic & Physical Chemistry, Indian Institute of Science, Bangalore , India jagirdar@ipc.iisc.ernet.in Contents Figure 1. 1 H NMR spectrum of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) in CD 2 Cl 2 at room temperature Figure P{ 1 H} NMR spectrum of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) in CD 2 Cl 2 at room temperature Figure C{ 1 H} NMR spectrum of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) in CD 2 Cl 2 at room temperature Figure 4. 1 H NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature Figure P{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature Figure C{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature Figure F NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature Figure 8. 1 H NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature Figure P{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature Figure C{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature Figure F NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature S1

2 Figure 12. Variable temperature 1 H NMR spectral stack plot (hydride region) of cis, trans- [RuH(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CDCl 2 F/CDClF 2. Figure 13. Variable temperature 1 H NMR spectral stack plot (hydride region) of cis, trans- [RuH(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2. Figure 14. Variable temperature T 1 measurements of cis, trans-[ruh 2 (PPh 3 ) 2 (bpy)] (1) in CD 2 Cl 2 at 400 MHz. Figure 15. Variable temperature T 1 measurements of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) (right) in CD 2 Cl 2 at 400 MHz. Figure H NMR spectra (hydride region) of the isotopomers of cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at 296 K; acquired using a 500 MHz instrument Figure H NMR spectra (hydride region) of the isotopomers of cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at 296 K; acquired using a 500 MHz instrument. Figure H NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature Figure P{ 1 H} NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature Figure C{ 1 H} NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature Figure F NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature Figure 22. IR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) Figure H NMR spectral stack plot of the reaction between cis, trans- [RuH 2 (PPh 3 ) 2 (bpm)][otf] (2) and CH 3 OTf in CD 2 Cl 2 at 203 K. Figure P{ 1 H} NMR spectral stack plot of the reaction between cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) and Et 3 N (2 equiv) in CH 2 Cl 2 (CDCl 3 external lock) at room temperature Figure H NMR spectral stack plot of the reaction between cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) and Et 3 N (2 equiv) in CH 2 Cl 2 (CDCl 3 external lock) at room temperature Calculation of ΔG of the exchange process in 1a and 2a Figure 26. ln (W ½ 30) vs 1/T plot of 1a Figure 27. ln (W ½ 30) vs 1/T plot of 2a Calculation of T 1 (min) of the H 2 ligand of 1a and 2a S2

3 Figure 1. 1 H NMR spectrum of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) in CD 2 Cl 2 at room temperature Figure P{ 1 H} NMR spectrum of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) in CD 2 Cl 2 at room temperature S3

4 Figure C{ 1 H} NMR spectrum of cis, trans-[ruh 2 (PPh 3 ) 2 (bpm)] (2) in CD 2 Cl 2 at room temperature S4

5 Figure 4. 1 H NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature S5

6 Figure P{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature Figure C{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature S6

7 Figure F NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpy)][otf] (1a) in CD 2 Cl 2 at room temperature S7

8 Figure 8. 1 H NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature S8

9 Figure P{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature Figure C{ 1 H} NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature S9

10 Figure F NMR spectrum of cis, trans-[ruh(η 2 -H 2 )(PPh 3 ) 2 (bpm)][otf] (2a) in CD 2 Cl 2 at room temperature S10

11 Electronic Supplementary Material (ESI) for Dalton Transactions Figure 12. Variabble temperatture 1H NM MR spectral stack plot (hydride reegion) of ciss, trans[ruh(ηη2-h2)(pph3)2(bpy)][ot Tf] (1a) in C CDCl2F/CD DClF2. S11

12 Electronic Supplementary Material (ESI) for Dalton Transactions Figure 13. Variabble temperatture 1H NM MR spectral stack plot (hydride reegion) of ciss, trans[ruh(ηη2-h2)(pph3)2(bpm)][ot Tf] (2a) in C CD2Cl2. Figure 14. Variabble temperaature T1 meeasurementss of cis, tra ans-[ruh2(ppph3)2(bpy))] (1) in CD2Cl2 at 400 MH Hz. S12

13 Electronic Supplementary Material (ESI) for Dalton Transactions Figure 15. Variabble temperaature T1 m measurementts of cis, trans-[ruh t H2(PPh3)2(bp pm)] (2) a 400 MHz. (right) iin CD2Cl2 at Figure 16. 1H NM MR spectraa (hydride region) of the isotopomers of ccis, trans-[r RuH(η2H2)(PPhh3)2(bpy)][O OTf] (1a) in n CD2Cl2 at 296 K; acq quired using g a 500 MHzz instrumen nt. S13

14 Figure H NMR spectra (hydride region) of the isotopomers of cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpm)][ OTf] (2a) in CD 2 Cl 2 att 296 K; acquired usingg a 500 MHz instrument. S14

15 Figure H NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature S15

16 Figure P{ 1 H} NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature S16

17 Figure C{ 1 H} NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature S17

18 Figure F NMR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) in CDCl 3 at room temperature Figure 22. IR spectrum of cis, trans-[ruh(co)(pph 3 ) 2 (bpm)][otf] (2b) S18

19 Electronic Supplementary Material (ESI) for Dalton Transactions Figure H NMR sp pectral stacck plot of o the reaaction bettween cis, trans- [RuH2(P PPh3)2(bpm m)][otf] (2)) and CH3O Tf in CD2Cl C 2 at 203 K. S19

20 Figure P{ 1 H} NMR spectral stack plot of the reactionn between cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpm)][ OTf] (2a) and Et 3 N (2 equiv) in CH 2 Cl 2 (CDCl 3 external lock) at room temperature S20

21 Figure H NMR spectral stack plot of the reaction between cis, trans-[ruh(η 2 - H 2 )(PPh 3 ) 2 (bpm)][ OTf] (2a) and Et 3 N (2 equiv) in CH 2 Cl 2 (CDCl 3 external lock) at room temperature Calculation of ΔGG of the exchange process in 1a and 2a Rate constant of the exchangee process above T C is written as K a = [π (Δν) 2 ] / 2 ( W ½ W 0 ½) Ref: Belci, M. Basic 1 H and 133 C NMR Spectroscopy,, Elsevier 2005, p213. where, K = Rate constant of the scrambling process Δν = Chemical shift differencee between dihydrogen and hydridee in Hz W ½ = Full width at half maxim of the scrambling system W 0 ½ = W ½ when there is no scrambling (reference) T C = Coalescence temperaturee K a = [π (Δν) 2 ] / 2 ( W ½ W 0 ½) S21

22 = A e (ΔG )/RT [Arrhenius equation, A = Frequency factor] Simplification gives ln (W ½ W 0 ½) = (ΔG /R)(1/T) + C [C = Constant] We assume that W 0 1/2 of the hydride signal of 1a and 2a are same as that of 1 and 2 respectively in their 1 H NMR spectrum. W 0 ½= 30 Hz (FWHM of hydride signal of 1 or 2) The above assumption is required since we did not observe decoalescence of the RuH 3 signal of 1a and 2a. ln (W ½ 30) = [ΔG (approx)/r][1/t] + C Slope of ln (W ½ 30) vs 1/T plot will give ΔG (approx) Assumptions: 1. Free energy of activation does not change with temperature 2. Change in line broadening is a measure of change in rate of the exchange process Figure 26. ln (W ½ 30) vs 1/T plot of 1a S22

23 Figure 27. ln (W ½ 30) vs 1/T plot of 2a Calculation of T 1 (min) of the H 2 ligand of 1a and 2a The relaxation rate (R H3 ) of the RuH 3 moieties of complexes 1a and 2a could be written as the weighted average of that of the individual hydride and η 2 -H 2 ligands i.e., R H3 = (R H + 2R H2 )/3 where, R H = relaxation rate of the hydride ligand caused by rest of the molecule, and R H2 = relaxation rate of the η 2 -H 2 ligand. R H2 has two components: (i) R M i.e., mutual relaxation of the two H-atoms of the η 2 -H 2 ligand and (ii) R R i.e., relaxation of the η 2 -H 2 ligand caused by rest of the molecule. Among these two components, R M is actually related to T 1 (min) of the η 2 -H 2 ligand, i.e., T 1 (H 2 ). Therefore, R H3 = {R H + 2(R M + R R )}/3 Or, R H3 = (3R H + 2R M )/3 [since, R R ~ R H ] Now, we know that T 1 = (1/R), therefore, the above equation can be written in terms of T 1 (min) of the η 2 -H 2 ligand as, 1/T 1 (H 2 ) = (3/2){1/T 1 (RuH 3 ) 1/T 1 (RuH 2 )} where, T 1 (RuH 3 ) is the T 1 (min) of complexes 1a and 2a, T 1 (RuH 2 ) is the T 1 of complexes 1 and 2 at respective temperatures (183 K for 1a and 191 K for 2a). S23