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Ion–Molecule Reactions of “Rollover” Cyclometalated [Pt(bipy−H)] + (bipy=2,2′‐bipyridine) with Dimethyl Ether in Comparison with Dimethyl Sulfide: An Experimental/Computational Study
Author(s) -
Butschke Burkhard,
Ghassemi Tabrizi Shadan,
Schwarz Helmut
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902742
Subject(s) - chemistry , dimethyl ether , molecule , dimethyl sulfide , ether , medicinal chemistry , sulfur , platinum , ion , photochemistry , inorganic chemistry , organic chemistry , catalysis
The ion–molecule reactions of dimethyl ether with cyclometalated [Pt(bipy−H)] + were investigated in gas‐phase experiments, complemented by DFT methods, and compared with the previously reported ion–molecule reactions with its sulfur analogue. The initial step corresponds in both cases to a platinum‐mediated transfer of a hydrogen atom from the ether to the (bipy−H) ligand, and three‐membered oxygen‐ and sulfur‐containing metallacycles serve as key intermediates. Oxidative CC bond coupling (“dehydrosulfurization”), which dominates the gas‐phase ion chemistry of the [Pt(bipy−H)] + ion with dimethyl sulfide, is practically absent for dimethyl ether. The competition in the formation of C 2 H 4 and CH 2 X (X=O, S) in the reactions of [Pt(bipy−H)] + with (CH 3 ) 2 X (X=O, S) as well as the extensive H/D exchange observed in the [Pt(bipy−H)] + /(CH 3 ) 2 O system are explained in terms of the corresponding potential‐energy surfaces.