Decomposition pathways of platinum(II) complexes containing alkyl and halide ligands investigated by electrospray mass spectrometry. The X-ray crystal structure of cis-[PtCl{CH2C(O)CH2Cl}(PPh3)2]
作者： William Henderson , John Fawcett , Raymond D.W. Kemmitt , Peter McKenna , David R. Russell
DOI: 10.1016/S0277-5387(96)00570-0
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摘要: Abstract The platimun(II) alkyl-halide complexes cis[PtCl{CH2C(O)CH2Cl}(PPh3)2], cis- [PtCl{CH2C(O)CH3}(PPh3)2], trans-[PtI(Me)(PPh3)2], [Pt{EtSCH2C(O)CH2}Br(PPh3)] and [Pt{MeSCH2C(O)CH2}I(PPh3)] have been investigated by electrospray mass spectrometry (ESMS). For all complexes, loss of halide ion provides the initial ionization pathway resulting ions may contain coordinated ligands from solvent (acetonitrile, ammonia added pyridine). At high cone voltages, undergo cyclometallation one triphenylphosphine ligands. However, for chloroacetonyl complex cis-[PtCl{CH2C(O)CH2Cl}(PPh3)2], fragmentation to [PtCl(PPh3)2]+ preceeds cyclometallation. It is proposed that this fragments via oxidative addition CCl bond, forming an unstable platina (IV)cyclobutan-3-one (oxodimethylenemethane) complex, which undergoes reductive elimination cyclopropanone. X-ray crystal structure cis-[PtCl{CH2C(O)CH2Cl}(PPh3)2] also reported.
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