Hydrido carbonyl complexes, preparation

The chemistry of the metal carbonyl hydrides and metal carbonylates remained the principal research topic for Hieber until the 1960s. He mentioned in his account [25], that it was a particular pleasure for him that in his laboratory the first hydrido carbonyl complexes of the manganese group, HMn(CO)5 and HRe(CO)5, were prepared by careful addition of concentrated phosphoric acid to solid samples of the sodium salts of the [M(CO)5] anions, giving the highly volatile hydrido derivatives in nearly quantitative yield [45, 46]. In contrast to HCo(CO)4 and its rhodium and iridium analogues, the pentacarbonyl hydrido compounds of manganese and rhenium are thermally remarkably stable, and in... 

Hydrogen can be generated from formic acid-amine adducts at room temperature, and used directly in fuel cells [126,127]. Ruthenium metal carbonyl and hydrido carbonyl complexes exhibit a catalytic activity in the decarboxylation of formic acid. Hence, [Ru4(CO)i2H4] prepared from RUCI3 and formic acid can decompose formic acid to hydrogen and carbon dioxide [126]. 

Hydrido-carbonyl and -phosphine complexes. Several new hydrido-diphenyl-phosphine complexes have been prepared from the recently described cis- or trans- [RuCl2(HPPh2)4] (Scheme 3). 

Hydrido-carbonyl and -phosphine complexes. A series of hydride complexes [IrHCl(PPh3)2(RCOO)] (R = Me, Et, Pr, H, Ph, CF3, MeCHCl, or P-NO2-CgH4) (44) have been prepared via the protonation of [Ir(N2)Cl(PPh3)2] w ith... 

In addition to the protonalion route, hydrido complexes may be prepared by reaction of carbonyl complexes with hydride donors ... 

Owing to high reactivity, hydrido complexes are utilized in the synthesis of compounds which either cannot be prepared or are prepared with difficulty in a different way. For example, tetrafluoroethylene reacts with hydrido carbonyls to give CF2CF2H complexes ... 

Phosphine-substituted hydrido-silyl complexes [FeH(SiR)3(CO)sL] have been prepared by carbonyl substitution in cis-[FeH(SiR3)(CO)4] thus for example, reaction of 1 equivalent of dppm with cis-[FeH(Si(0He)3 (CO)4] leads to mer-[FeH(Si(OHe)3)(CO)3(dppm-P)] and the reaction of cis-[FeH(SiPh3)(CO)4] with Ph2P(CH2)4PPh2 (dppb) leads to mer-[FeH(SiPh3)(CO)3(dppb-P)]. ... 

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