Double Oxidative Addition of Tin(IV) Halides to Platinum(II): Complexes with Pt−Sn and Pt−Sn−Pt Linkages

Citations Over TimeTop 19% of 2001 papers

Abstract

The electron-rich organoplatinum complex [PtMe2(bu2bpy)], 1, bu2bpy = 4,4‘-di-tert-butyl-2,2‘-bipyridine, undergoes easy oxidative addition of a Sn−Cl bond of PhnSnCl4-n to give the corresponding stannylplatinum(IV) complexes [PtClMe2(SnPhnCl3-n)(bu2bpy)], 2, n = 0; 3, n = 1; 4, n = 2; 5, n = 3. Further reaction of 1 with 2 or 3 can occur to give the μ-stannylene complexes [{PtClMe2(bu2bpy)}2(μ-SnPhnCl2-n)], 6, n = 0; 7, n = 1, the first time that μ-stannylene complexes have been prepared by oxidative addition of Sn−Cl bonds. In all cases, the oxidative additions of Sn−Cl bonds to platinum(II) occurred with trans stereochemistry. The products are characterized by NMR spectroscopy and, in most cases, by X-ray structure determinations. Trends in coupling constants [especially 1J(PtSn)] and bond distances and angles give insight into structure and bonding in the series of complexes. Complex 2 was cocrystallized with the organotin compound [Me2SnCl2.Me2SnO]2. The oxidative addition of GeCl4 to complex 1 occurs with cis-stereochemistry to give [PtClMe2(GeCl3)(bu2bpy)], which does not react with more complex 1 to give a μ-germylene complex.

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