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The reaction of Pt (PiPr 3) 3 with SO 2 led to the formation of (PiPr 3) 2 Pt (SO 2) (1), isolated in 93% yield. The addition of H (OEt 2) 2 + BAr f (BAr f = B (3, 5- (CF 3) 2 C 6 H 3) 4) to 1 in ether at −78 °C afforded the solvent complex trans - (PiPr 3) 2 Pt (H) (OEt 2) BAr f (2) in 85% isolated yield. Complex 2 served as a precursor to monodentate halocarbon complexes of the type Pt (η 1 -XR). The dichloromethane complex trans - (PiPr 3) 2 Pt (H) (η 1 -ClCH 2 Cl) BAr f (3) was isolated in 80% yield by the recrystallization of 2 from CH 2 Cl 2 /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 - (PiPr 3) 2 Pt (H) (η 1 -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 - (PiPr 3) 2 Pt (H) 2 (μ-I) BAr f (6) which was structurally characterized. The THF adduct (PiPr 3) 2 Pt (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 CH 2 Cl 2 complex 3 reacted with H 2 to form the dihydrogen complex trans - (PiPr 3) 2 Pt (H) (η 2 -H 2) BAr f which was characterized by NMR spectroscopy.
Butts et al. (Mon,) studied this question.