79813-73-3

Upstream product

• 62987-80-8 Pt₃*3CO*3P(C₆H₁₁)3 = [Pt₃(CO)3(P(C₆H₁₁)3)3] 
• 847025-79-0 [Pt3I(μ-I)(μ-CO)2(PCy3)3] 
• 847025-76-7 [Pt₂I(CO)2(PCy₃)2(CH₂CN)] 
• 624-75-9 iodoacetonitrile 
• 847025-77-8 [Pt₂I₂(CO)2(PCy₃)2] 

Relevant academic research and scientific papers

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

The reaction of [Pt3(μ-CO)3(PCy3) 3] (1) with one mole-equivalent of iodo-acetonitrile was quantitative at - 70 °C giving the oxidative addition product [Pt 3(μ-CO)3(PCy3)3(I)(CH 2CN)] (2). Fragmentation of 2 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 1 with one mole-equivalent of halogens X2 gave the new 44-electron clusters [Pt3X(μ-CO)2(μ-X)(PCy3)3] (X = I2 (7a) or Br2 (7b)) by oxidative addition followed by substitution of CO by X-. Fragmentation of 7a and 7b took place in solution when using one and a half mole-equivalents of X2 giving dimers 4a and [Pt2Br2(CO)2(PCy 3)2] (4b) as well as [Pt2X 2(μ-X)2(CO)2(PCy3)2]. Monomers cis-[PtX2(CO)(PCy3)] were the final products of the reaction of 1 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 SnCl2·2H2O were added to a solution of 4a or its chloro-analogue giving [Pt2X2(μ-SnCl 2)(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.