All the possible three O,O‘-,
O,S-, and S,S‘-chelation modes were observed for
diamineplatinum(II) complexes of sulfur-containing dicarboxylate
ligands
S−(CH2)
n
−S−CC(COO-)2
(n = 2, 3, 4) depending on their dithioether ring size.
Such variable coordination modes are explicable in terms of their
ring size effects affording different degrees of contribution to the
resonance structures of the planar C2CCS2
moiety, which gives rise to dramatic change in the basicity of the ring
sulfur atoms competing with the carboxylate oxygen atoms for
coordination to
patinum(II).
Studies by 3,P NMR spectroscopy have shown that the face-sharing bioctahedral molecules Rh2X6(PR3)3 (X = Cl, Br; PR3 = PEt3, PPr3, PBu3) exist exclusively as the 1,2,6-isomers and are converted by addition of 1 molar equiv of PR'3 (R' may be R) exclusively to the l,3,6,8-Rh2X6(PR3)3(PR'3) isomer, with the entering PR'3 occupying the 6-(or 8-) position. Moreover, the edge-sharing 1,3,6,8-Rh2X6(PR3)4 type molecules react further with trialkylphosphine to produce exclusively mer-RhX3(PR3)3 products, even though, as is also demonstrated, the/ac-RhX3(PR3)3 isomers are thermodynamically preferred.
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