Carbon dioxide activation; formation of trans-(Ph₃P)₂Rh(CO)(OCO₂H) in the reaction of CO₂with HRh(CO)(PPh₃)₃–CO and the determination of its structure by X-ray crystallography

Abstract

The intermediate produced from the interaction of HRh(C0) (PPh,), with CO reacts with carbon dioxide to yield a novel hydrogencarbonate complex, trans-( Ph,P),-Rh(C0) (OC0,H) (1) , whose structure has been established by X-ray crystallography; (1) undergoes reversible loss of CO,.-_

Action of triphenylphosphine on [Rh(HCOO)(PPh3)2(CO)]. A novel synthetic route to [HRh(PPh3)3(CO)]

“…[HRhL n ] + CO 2 conversion observed by Leitner and other authors [5,6]. Mechanistic aspects of related reactions and of the reverse CO 2 insertion into the M-H bond are discussed extensively [5][6][7][8][9][10][11][12].…”

Interaction of Carbon Dioxide with [IrH2{(tBu2)PCH2CH2CHCH2CH2P(tBu2)}]

“…Nicholas reported the bicarbonate resonance at δ 7.25 for [Rh(κ 2 -O 2 COH)(CO)-(Ph 3 P) 2 ]. 41 An infrared spectrum of the bicarbonate complex showed a very weak Ir-H band at 2000 cm -1 and υ (asym) (CO 2 -) carbonate band at 1587 cm -1 and υ (sym) (CO 2 -) at 1469 cm -1 which is similar to the known Rh complex, reported by Ibers and Otsuka. 40 The O 2 COH vibrations ν( Η) at 2652 and 2696 cm -1 are similar 40,42,43 as well.…”

Bioinorganic Chemistry of Group 12 Complexes Supported by Tetradentate Tripodal Ligands Having Internal Hydrogen‐Bond Donors

“…[14,38] Interestingly, several isolated mononuclear metal hydrogen carbonate complexes also demonstrate both hydrogen-bond-donor and -acceptor interactions involving the metal-bound hydrogen carbonate ligand. [39][40][41][42][43] To date, a mononuclear zinc hydrogen carbonate complex of relevance to carbonic anhydrase has not been structurally characterized. However, Masuda and co-workers recently reported that a zinc hydroxide complex of the tnpa chelate ligand {[(tnpa)Zn-OH]ClO 4 , Figure 5} undergoes reaction in the presence of CO 2 to produce a putative zinc hydrogen carbonate complex, which has been characterized by 1 H and 13 C NMR and electrospray mass spectrometry.…”