Reaction of the new tridentate ligand (o-(Ph2P)C6H4)2SbPh (referred to as L) with (Et2S)2PtCl2 affords a complex LPtCl2 (1 ) that feature a unique C-Sb-Pd-Cl.  Formation of this complex, which results from the oxidative insertion of the antimony in a Pt-Cl bond has been confirmed by NMR and X-ray analysis.  Remarkably, complex 1  can be oxidized with o-chloranil (o-O2C6Cl4) to afford a tetravalent platinum stiboranyl complex (2 ) which has also been fully characterized.  One of the key features of this complex is the presence of a covalent Pt-Sb bond of 2.59 �.  Remarkably, a simple chloride for fluoride anion exchange induces a major structral change, with the platinum center reverting to the divalent state (3 ).  This anion induced internal redox process, which is accompanied by dissociation of the Pt-Sb bond, is fully reversible.

Development of platinum(II) and -(IV) complexes with bisphosphanylstibine ligand

243rd National Meeting (2012)

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