Platinum-Mediated Coupling of Methane and Small Nucleophiles (H2O, PH3, H2S, CH3NH2) as a Model for C−N, C−O, C−P, and C−S Bond Formation in the Gas Phase

The reactions of Pt + and PtCH 2 + with the nucleophiles H 2 O, PH 3, H 2 S, HCl, CH 3 NH 2, and CH 3 OH are studied by Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry. In the reactions of PtCH 2 +, carbon−heteroatom bond formation can be accomplished for all substrates except CH 3 OH and HCl. The reaction of PtCH 2 + with two molecules of water yields Pt(CO)(H 2 O) + and constitutes a gas-phase model for the platinum-mediated generation of water gas according to CH 4 + H 2 O → CO + 3H 2 . In the reactions with PH 3 and H 2 S, carbon−phosphorus and carbon−sulfur bond formation to PtCPH + and PtCS + competes with demethanation and dehydrogenation of the substrates to yield PtS n + ( n = 1−4) and PtP n H m + ( n = 1−6; m = 0−3) compounds, respectively. For organic nucleophiles such as CH 3 NH 2 and CH 3 OH, C−N and C−O coupling is much less efficient than platinum-mediated C−H bond activation of the substrates.