Polyhedron p. 873 - 879 (1996)
Update date:2022-07-29
Topics:
Danopoulos, Andreas A.
Wilkinson, Geoffrey
Sweet, Tracy K. N.
Hursthouse, Michael B.
The chromium(VI) imidothiolato complex, Cr(Nmes)2(Smes)2 (1), mes = 2,4,6-Me3C6H2, reacts with 2,6-xylylisocyanide (xylNC) to form the five-coordinate chromium(IV) complex Cr(Nmes)(Smes)2(xylNC)2(2). A similar interaction of Cr(Nmes)2 (SC6H2-2,4,6-Pi3)2 gives only the disulfide adduct Cr(Nmes)2(SC6H2-2,4,6-Pri 3)2?(2,4,6-Pr13C 6H2S)2(3). Interaction of 1 and PMePh2 gives Cr4(Nmes)2(μ-Nmes)4(Smes) 2(O)2(μ-O)2(4), where the oxygen atoms arise from adventious oxygen during work up. The X-ray crystal structures of 2-4 have been determined. In 2 the CriIV centre has trigonal bipyramidal geometry with axial isocyanides. The CrVI centre in 3 is tetrahedral and 4 is a centro-symmetric tetramer in which the outer CrV centres are tetrahedral and the inner CrIV centres are square-pyramidal.
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