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. Author manuscript; available in PMC: 2014 Feb 5.
Published in final edited form as: Chem Rev. 2013 Jun 14;113(8):6621–6658. doi: 10.1021/cr300463y

Table 1.

Catalyst Precursors and Conditions for CO2 Hydrogenation to Formatea

catalyst precursor solvent additives H2/CO2 (atm) T (°C) TON TOF (h−1) ref
(PNPyP)IrH3 H2O KOH, THF 25/25 200 300 000 150 000 75n
RuCl(OAc)(PMe3)4 scCO2 NEt3, C6F5OH 70/120 50 31 667 95 000 75o
(PNPyP)IrH3 H2O KOH, THF 29/29 120 3 500 000 73 000 75n
[Cp*Ir(phen)Cl]Cl H2O KOH 29/29 120 222 000 33 000 75m
[Cp*Ir(OH2)(6HBPY)]2+ H2O KHCO3 5/5 120 12 500 25 200 75q
[Cp*Ir(OH2)]2(THBPM)4+ H2O KHCO3 20/20 50 153 000 15 700 75p
(PNHP)IrH2(O2CH) H2O KOH 27/27 185 348 800 14 500 75l
[{(tppms)2RuCl2}2] + 2 tppms H2O NaHCO3 60/35 80 9600 75k
(C6Me6)Ru(bis-NHC)Cl H2O KOH 20/20 200 2500 2500 75d
RuH2(PMe3)4 scCO2 NEt3, H2O 85/120 50 7200 1400 75g
Fe(BF4)2·6H2O + (PP3) MeOH NaHCO3 59/0 100 3850 770 75c
[RuCl2(C6H6)]2 + 4 dppm H2O NaHCO3, THF 79/0 70 1374 687 75j
Ru(PEt3)4(H)2 diols N(hex)3 81/33 50 659 659 75i
Ru2(CO)5(dppm)2 acetone NEt3 35/35 rt 207 207 75h
RhCl(PPh3)3 MeOH PPh3, NEt3 20/40 25 2500 125 75f
[Cp*Ir(OH2)]2(THBPM)4+ H2O NaHCO3 0.5/0.5 25 7200 64 75p
[Rh(cod)Cl]2 + dppb DMSO NEt3 20/20 25 1150 52 75e
NiCl2(dcpe) DMSO DBU 40/160 50 4400 20 75b
CpRu(CO)(μ-dppm)Mo(CO)2Cp C6H6 NEt3 30/30 120 43 1 75a
a

Abbreviations: DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene, dppm = CH2(PPh2)2, PP3 = tripodal tetraphosphine, dppb = Ph2P(CH2)4PPh2, dcpe = 1,2-C2H4[P(C6H11)2]2, cod = 1,5-cyclooctadiene, NHC = N-heterocyclic carbene ligand, tppms = P(C6H4-3-SO3Na)3, phen = 9,10-phenanthroline, PNHP = (i-Pr2PC2H4)2NH, PNPyP = C5H3N-2,6-[CH2P(i-Pr)2]2, THBPM = 4,4′,6,6′-tetrahydroxy-2,2′-bipyrimidine, 6HBPY = 6,6′-dihydroxy-2,2′-bipyridine, L = 4-(1-H-pyrazol-1-yl-κN2)benzoic acid-κC3).