184361-41-9Relevant academic research and scientific papers
Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr3)2PtH(η1-XR)]BAr(f) and analogues with Et2O, THF, and H2 ligands, halide-to-metal π bonding in halocarbon complexes
Butts, Matthew D.,Scott, Brian L.,Kubas, Gregory J.
, p. 11831 - 11843 (2007/10/03)
The reaction of Pt(PiPr3)3 with SO2 led to the formation of (PiPr3)2Pt(SO2) (1), isolated in 93% yield. The addition of [H(OEt2)2]+BAr(f) (BAr(f) = B(3,5-(CF3)2C6H3)4) to 1 in ether at -78°C afforded the solvent complex trans-[(PiPr3)2Pt(H)(PEt2)]BAr(f) (2) in 85% isolated yield. Complex 2 served as a precursor to monodentate halocarbon complexes of the type Pt(η1-XR). The dichloromethane complex trans-[(PiPr3)2Pt(H)(η1-ClCH2Cl)]BAr(f) (3) was isolated in 80% yield by the recrystallization of 2 from CH2Cl2/hexane. IR spectroscopy suggested the existence of dichloromethane binding which was confirmed by X-ray crystallography. The reaction of 2 or 3 with iodo- or bromobenzene led to the isolation of the haloarene complexes trans-[(PiPr3)2Pt(H)(η1-XPh)]BAr(f), where X = I (4, 87% yield) or Br (5, 60% yield). Both compounds were characterized spectroscopically and by X-ray crystallography. An unexpected steric interaction in 4, suggested by molecular mechanics calculations to be significant, was rationalized in terms of halide-to-metal π bonding. The PhI complex 4 decomposed under harsh conditions to the bridging iodide compound {trans-[(PiPr3)2Pt(H)]2(μ-I)]BAr(f) (6) which was structurally characterized. The THF adduct [(PiPr3)2Pt(H)(THF)]BAr(f) (7), isolated in 78% yield and also characterized by X-ray crystallography, was formed when any of the compounds 2, 3, 4, or 5 was dissolved in THF. The CH2Cl2 complex 3 reacted with H2 to form the dihydrogen complex trans-[(PiPr3)2Pt(H)(η2-H2)]BAr(f) which was characterized by NMR spectroscopy.
