CO2 insertion into M-OH bonds

More details about the reactivity of the M-H C02 system can be found in Chap. 8, where the electrochemical, photochemical, and electrophotochemical reduction of CO2 in water is discussed. 

The complex is reported to be strictly monomeric as the steric hindrance of the ligand prevents any association in solution. The reaction is first order in [COJ as shown in Fig. 4.1. It is also first order in [Ni] so that the overall second order is obtained as shown in (4.13)  

Several other transition metal-hydroxo systems have been investigated. The insertion reaction affords in general a hydrogen carbonate species (4.14) which can be stable or can react further. 

One of the earliest reported studies was made on lr(OH)(CO)(PPh3)2 [35] which was shown to undergo a 

The chemistry of hydroxo species is quite rich and of interest as it is relevant to several reactive systems in which (transition) metals-H20 and CO2 are present. This is, for example, the case of methane dry reforming or C02-mediated dehydrogenation of HCs or syngas utilization or other similar high temperature processes as those described in Chap. 7. 

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