By M.M. Taqui Khan
Activation Of Small Inorganic Molecules
summary: Activation Of Small Inorganic Molecules
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Extra resources for Activation of Small Inorganic Molecules
95) of hydrogen per atom of cobalt. The nature of the intermediate formed when pentacyanocobaltate(II) reacts with hydrogen was thoroughly investigated by King and Winfield [135,136], and Griffith and Wilkinson . A detailed spectroscopic study by King and 3 Winfield  has confirmed the formation of [HCo(CN) 5 ] ~ as one of the 3 intermediates when hydrogen is absorbed by [Co(CN) 5 ] ~. The hydrido complex is characterized by an absorption band at 305 nm that is absent in other cobalt(III) complexes.
The replacement of the tertiary phosphines by alkyl sulfides in the coordination sphere of rhodium thus alters to a considerable extent its catalytic properties. With maleic acid as a substrate, in tenfold excess, the rate of hydrogénation is first order with respect to the rhodium(III) complex and molecular hydrogen, and independent of the substrate concentration. In the absence of maleic acid, rhodium(III) is rapidly reduced to the metallic state. The initial reaction seems to involve the reduction of the rhodium(III) complex to a rhodium(I) by molecular hydrogen .
Reactions of RuCl 2 (PPh 3 ) 3 or a concentrated solution of RuCl 2 (PPh 3 ) 4 with molecular hydrogen gave a hydrido complex, RuClH(PPh 3 ) 3 , which is considered to be an active intermediate in the catalytic hydrogénation reaction. The co-catalyst, ethanol, may possibly be the source of hydride ion for the formation of the RuClH(PPh 3 ) 3 species, as evidenced by the very slow rate of hydrogénation in the absence of ethanol . The ruthenium complexes RuCl 2 (PPh 3 ) 3 and RuCl 2 (PPh 3 ) 4 dissociate in methanol-benzene solution to form solvated species according to the equilibria RuCl 2(PPh 3)4 , R u C l 2( P P h 3) 3S + P P h 3 (52) R u C l 2( P P h 3) 3 , R u C l 2( P P h 3) 2S 2 + P P h 3 (53) shown in Eqs.