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
In benzene solution, the initial rates of hydrogénation increased considerably in the presence of a basic co-solvent such as ethanol. With cyclohexene or 1-heptene as substrates, the rate of hydrogénation was first order with respect to alkene and catalyst concentrations. The catalytic activity of the ruthenium(II) complexes mentioned above was very much dependent on the ^-acceptor character of the neutral ligand L, decreasing in the order AsPh 3 > SbPh 3 > diphos. The same order of reactivity was observed  for L 3 RuCl(SnCl 3 ") complexes.
For aromatic systems, the concept of participation of metal π complexes in hydrogénation seems to be supported by the activation energies of hydrogénation of benzene, toluene, ethylbenzene, /7-xylene, and mesitylene on a nickel-magnesium oxide catalyst . The decrease in the activation energies in the metal-catalyzed hydrogénation of substituted benzenes parallels their relative donor tendencies toward metal ions. For homogeneous systems, the requirement for coordination of both π bonds and molecular hydrogen is satisfied by the platinum group metal ions platinum(ll) [152,153], ruthenium(II) [154-158], palladium(II) , and rhodium(I) [160,161].
The mechanism proposed 3 [ H 2C o ( C N ) 5] [ C o ( C N ) 5] - + H 2 3 3 [ H 2C o ( C N ) 5] - + [ C o ( C N ) 5] 6 [(CN) 5Co· · · Η Η· · C o ( C N ) 5 ] " 3 (35) 6 [(CN) 5Co- •Η····Η· - C o ( C N ) 5 ] 22 *-2 k3 3 2 [ H C o ( C N ) 5] " (36) (37) is very similar to that of King and Winfield  with the only difference that a binuclear hydrogen complex is proposed [143,144] as an intermediate. In this reaction with molecular hydrogen, pentacyanocobaltate(II) was described by the term "hydrogen carrier" .