Diplatinum complexes: Chemoselective reactions of the mu-orthometalated, metal-metal bonded complex [Pt-2(mu-o-C6H4PPh2)(mu-PPh2)(PPh3)(2)] with acids. Crystal structures of [Pt2Cl(mu-PPh2)(PPh3)(3)], [Pt2I(mu-PPh2)(PPh3)(3)], [Pt-2(mu-H)(mu-PPh2)I-2(PPh3)(2)] and cis,cis-[Pt-2(mu-I)(mu-PPh2)I-2(PPh3)(2)]

作者：Archambault Christine; Bender Robert; Dusausoy Yves; Welter Richard; Braunstein Pierre^*

来源：Polyhedron, 2013, 52: 545-552.

DOI：10.1016/j.poly.2012.08.030

• Diplatinum complexes
• Metal-metal bonds
• Platinum
• Phosphido ligands
• Protonation

In order to investigate further the chemoselectivity of reactions involving the mu-orthometalated, metal-metal bonded dinuclear Pt(I) complex [Pt-2(mu-o-C6H4PPh2)(mu-PPh2)(mu-PPh3)(2)](Pt-Pt) (1), it was reacted with HCl and HI using various stoichiometries. The first step was the breaking of the metal-carbon bond and the formation of C-H and Pt-X bonds. When a 1:1 ratio was used, the complexes [Pt2X(mu-PPh2)(PPh3)(3)] (Pt-Pt) (2, X = Cl; 3, X = I) have been obtained but the use of a 2:1 ratio resulted instead in the formation of the complexes [Pt-2(mu-H)(mu-PPh2)X-2(PPh3)(2)](Pt-Pt) (4, X = Cl; 6, X = I). The latter transformed into [Pt-2(mu-X)(mu,-PPh2)X-2(PPh3)(2)] (5, X = Cl; 7, X = I) in the presence of an additional equivalent of HX. The cis,cis- and cis,trans-isomers of 7 were also obtained by oxidation of 3 with one equivalent of iodine. Whereas compounds 4, cis,cis-5, and cis,trans-7 have been characterized in solution, the complexes 2.1/2C(7)H(8), 3, 6 and cis,cis-7 have been isolated and structurally characterized by X-ray diffraction.

• 出版日期2013-3-22