Insertion of SnCl2 into Pt-Cl bonds: synthesis and characterization of four- and five-coordinate trichlorostannylplatinum(II) complexes

Author： Momeni Badri Baleh Leili Jalili Hamzeh Saeideh Rominger Frank

Publisher： Taylor & Francis Ltd

ISSN： 0095-8972

Source： Journal of Coordination Chemistry, Vol.60, Iss.3, 2007-01, pp. : 285-293

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Abstract

Reaction of platinum(IV) chloride with SnCl2 · 2H2O in the presence of [NHR3]3Cl (R = Me, Et) in 3M hydrochloric acid affords the anionic five-coordinate platinum(II) complexes [NHR3]3[Pt(SnCl3)5], R = Me (1), Et (2), respectively. Moreover, platinum(IV) chloride reacts with SnCl2 · 2H2O in the presence of bis(triphenylphosphoranylidene)ammonium chloride in acetone/dichloromethane to form [N(PPh3)2]3[Pt(SnCl3)5] (3). In contrast, reaction of an acetone solution of platinum(IV) chloride with SnCl2 · 2H2O in the presence of bis(triphenylphosphoranylidene) ammonium chloride resulted in the formation of cis-[N(PPh3)2]2[PtCl2(SnCl3)2] (4). The same products are obtained by using a platinum(II) salt as starting material. Similarly, cis and trans- dichlorobis(diethyl sulfide)platinum(II) reacts with SnCl2 · 2H2O in 5M hydrochloric acid to give [PtCl(SEt2)3]3[Pt(SnCl3)5] (5) by facile insertion of SnCl2 into the Pt-Cl bond. However, treatment of an acetone solution of cis- and trans-[PtCl2(SEt2)2] with SnCl2 · 2H2O in the presence of a small amount of HCl resulted in the formation of 5, which dissociates in solution to give [PtCl2(SEt2)2]. The complexes have been fully characterized by elemental analysis and multinuclear NMR (1H, 13C, 195Pt, 119Sn) spectroscopy. A structure determination of crystals grown from a solution of 2 by X-ray diffraction methods shows that platinum adopts a regular trigonal bipyramidal geometry.