By M.M. Taqui Khan
Activation Of Small Inorganic Molecules
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Additional resources for Activation of Small Inorganic Molecules
ACTIVATION OF MOLECULAR HYDROGEN TABLE VI CONJUGATED AND ^ - U N S A T U R A T E D COMPOUNDS REDUCED BY HYDRIDOPENTACYANOCOBALTATE(III) Substrate CH 2—CH—CH—CH2 Product C H 3— C H 2— C H — C H 2 H 3C \ / c=c / \ References 128 H C H 2= C H — C ( C H 3) = C H 2 H CH3 C H 3— C H — C ( C H 3) = C H 2 C 6H 5C H = C H C O O H C H 3— C H = C H — C H = C H C O O H C6H5CH=CH2 C eH 5C ( C H 3) = C H 2 C 6H 5C ( C O O - ) = C H 2 C 6H 5C H = C H C H 2O H C H 2= C ( C H 3) C O O - C 6H 5C H 2— C H 2C O O H C H 3— C H = C H — C H 2— C H 2C O O H C6H5CH2—CH3 C 6H 5C H ( C H 3) — C H 3 C 6H 5C H ( C O O - ) — C H 3 C e H s C H 2C H 2C H 2O H C H 3— C H — C O O - 128,129, 146 129 128 128 128 128 128 1 C H 3C H = C H — C H O C H 3C H = C ( C H 3) — C H O C H 2= C — C O O " J C H 2C O O - 3 C H 3 C HC2H CH 2— C H O C H 3C H 2— C H ( C H 3) — C H O C H 3C H — c o o - 128 128 128 C H 2C O O " 128 128 C 6H 5C H 2— C — C O O H C 6H 5C H 2— C H — C O O H 129 ΝΟΗ C H 3— C — C O O H NH2 C H 3— C H — C O O H 129 II NOH I NH2 the τΓ-allyl complex 25 leading to the formation of 1-butene.
The hydrido complex is characterized by an absorption band at 305 nm that is absent in other cobalt(III) complexes. The complex has also been isolated as the cesiumsodium salt, Cs 2Na[HCo(CN) 5], by Banks and Pratt , and was characterized by its ultraviolet and infrared spectra. These investigators also identified another possible catalytically active intermediate, the dihydro 3 complex, H 2 Co(CN) 4 ~, as well as the probably inactive hexacyanocobaltate3 (III) ion, Co(CN) 6 ". Based on the Raman spectrum of a solution of pentacyanocobaltate(II) in aqueous methanol, a slightly distorted square-pyramidal geometry has been assigned  to this complex.
35)-(37)] on the grounds that chemical bonding of the intermediates 19 and 22 is virtually impossible. Except for a very unstable transition state and hydrogen bonding to electronegative atoms, bis-covalent hydrogen is not considered possible. Thus the intermediate 19 and 22 do not serve the desired purpose of eliminating a termolecular step in the process. On the other hand, the binuclear intermediate 21 proposed by deVries seems quite feasible and has analogies in the dicobalt and dimanganese carbonyls.
Activation of Small Inorganic Molecules by M.M. Taqui Khan