Oxidative addition of iodo-acetonitrile and of elemental halogens to [Pt3(mu-CO)3(PCy3)3

The reaction of Pt3(mu-CO)3(PCy3)3](1) with one mole-equivalent of iodo-acetonitrile was quantitative at -70 degrees C giving the oxidative addition product Pt3(mu-CO)3(PCy3)3(I)(CH2CN)](2). Fragmentation of was observed in solution giving Pt2I(CH2CN)(CO)2(PCy3)2](3) which is the major product at room temperature if the starting cluster/reactant ratio is equal to or less than 1 to 1.5. Dimer 3 decomposes slowly in solution giving Pt2I2(CO)2(PCy3)2](4a) and succinonitrile. Monomer PtI(CH2CN)(CO)(PCy3)] was the final product of the reaction when using excess of iodo-acetonitrile. The reactions of with one mole-equivalent of halogens X2 gave the new 44-electron clusters Pt3X(micro-CO)2(micro-X)(PCy3)3](X = I2(7a) or Br2(7b)) by oxidative addition followed by substitution of CO by X-. Fragmentation of and took place in solution when using one and a half mole-equivalents of X2 giving dimers 4a and Pt2Br2(CO)2(PCy3)2](4b) as well as Pt2X2(mu-X)2(CO)2(PCy3)2]. Monomers cis-PtX2(CO)(PCy3)] were the final products of the reaction of with excess of halogens. Insertion of SnCl2 was observed into the Pt-Pt bond but not into the Pt-X bond, when equimolar amounts of SnCl2 x 2H2O were added to a solution of 4a or its chloro-analogue giving Pt2X2(micro-SnCl2)(CO)2(PCy3)2]. The Pt(I) dimers have unusually small J(Pt-Pt) values as observed by 195Pt NMR and calculated by DFT. These values showed periodic changes comparing 4a and its analogues with other halides and mixed halide dimers.