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• W1988652022 abstract "The complexes [Co(NH3)5NCS]2+ and [Co(CN)5 SCN]3− have frequently been cited as classic examples of symbiotic bonding in terms of the Hard/Soft Acid/Base Principle. The results of infrared and electronic spectral studies in our laboratory have revealed that this comparison is appropriate only in protic solvents, for the [Co(CN)5SCN]3− complex isomerizes to its N-bonded isomer in CH2Cl2, acetone, and nitrobenzene. In DMF, an equilibrium is established involving the N-bonded isomer and a species resulting from the dissociation of the SCN- group. Dissociation is essentially complete in CH3CN and DMSO. S-bonding prevails in the protic solvent ethylene glycol, emphasizing the importance of H-bonding in stabilizing the S-bonded isomer. We have succeeded in preparing the corresponding [Co(CN)5SeCN]3− complex via an inner-sphere redox reaction between [Co(NH3)5 NCSe]2+ and [Co(CN)5]3− and find that it follows the same bonding pattern as a function of solvent as its thiocyanate analog. Infrared data indicate that the [Co (CN)5XCN]3− complexes isomerize via a dissociative mechanism, possibly involving the formation of an ion pair, in CH2Cl2, acetone, nitrobenzene, and DMF, the thiocyanate complex isomerizing at a faster rate. The rates of dissociation of the four [Co(CN)5CNX]3− linkage isomers in CH3CN and DMSO vary in the order: CoSCN > CoSeCN > CoNCS ∼ CoNCSe. The size of the countercation can determine the bonding mode adopted by the complexes in the solid state. S-bonding prevails when K+, Cs+, and CH3NH3+ are present, a mixture (25% N-bonded) is obtained with (CH3)2NH2+ and (CH3)4N+, like the previously reported (n-C4H9)4N+, yields only the N-bonded isomer." @default.
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• W1988652022 date "1975-01-01" @default.
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• W1988652022 title "Solvent and countercation effects on ambidentate bonding patterns in thiocyanato- and selenocyanatopentacyanocobaltate(III) complexes" @default.
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• W1988652022 doi "https://doi.org/10.1016/s0020-1693(00)93917-3" @default.
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