Thiocyanato complex dissociation

Borane, 1-methylbenzylaminocyanohydropyrrolyl-, 3, 84 Borane, thiocyanato-halogenohydro-, 3,88 Borane, trialkoxy-amine complexes, 3, 88 Borane, triaryl-guanidine complexes, 2,283 Borane, trifluoro-complexes Lewis acids, 3,87 van der Waals complexes, 3, 84 Borane complexes aminecarboxy-, 3,84 aminehalogeno-, 3, 84 amines, 3, 82, 101 B-N bond polarity, 3, 82 preparation, 3, 83 reactions, 3, 83 bonds B-N, 3, 88 B-O, 3, 88 B-S, 3, 88 Jt bonds, 3, 82 carbon monoxide, 3, 84 chiral boron, 3, 84 dimethyl sulfide, 3, 84 enthalpy of dissociation, 3, 82... 

Several complexes have beeai found to be dimeric. Infrared spectroscopy shows that the CuNCS(L) complexes (L = py, 2- or 4-picoline, 3,5-lutidine, or quinoline) contain bridging thiocyanato groups (332). The mass spectra of CuX P(cyclohexyl)3 complexes (X = Cl, Br, I) show no peaks of higher mass than those corresponding to dimeric molecules, and the far-infrared spectrum of the chloro complex indicates that they are dimeric with halo bridges (248). Triphenylphosphine reacts with copper(I) trifluoroacetate in dichloromethane to give [Cu(02C CF3)(PPh3)]2 which is dimeric in chloroform but partially dissociated in dichlorobenzene (107). 

Ligand Replacement Unidentate by Unidentate.—dissociative mechanism is proposed for the replacement of nitrito- or of thiocyanato-ligands in trans-[Co(dmgH)2(N02)2] and in rm/w-[Co(dmgH)2(NCS)2] respectively by thiourea. Thiocyanate is replaced much more rapidly than nitrite from these cobalt(m) centres. Substitution at bisdimethylglyoximatocobalt(m) complexes can be catalysed by cobalt(n) complexes. This has been demonstrated by the elucidation of the rate law for the cobalt(n)-catalysed reaction of trans-[Co(dmgH)2(PPhs)(NOa)] with pyridine ... 

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