Inorganica Chimica Acta p. 110 - 116 (2001)
Update date:2022-08-03
Topics:
Blosser, Patrick W.
Calligaris, Mario
Schimpff, David G.
Wojcicki, Andrew
Reactions of [(PPh3)2Pt(η3-CH2CCPh)]OTf with each of PMe3, CO and Br- result in the addition of these species to the metal and a change in hapticity of the η3-CH2CCPh to η1-CH2C≡CPh or η1-C(Ph)=C=CH2. Thus, PMe3 affords [(PMe3)3Pt(η1-C(Ph)=C=CH2)] +, CO gives both [trans-(PPh3)2Pt(CO)(η1-CH2 C≡CPh)]+ and [trans-(PPh3)2Pt(CO)(η1-C(Ph)=C=CH 2)]+, and LiBr yields cis-(PPh3)2PtBr(η1-CH2 C≡CPh), which undergoes isomerization to trans-(PPh3)2PtBr(η1-CH2 C≡CPh). Substitution reactions of cis- and trans-(PPh3)2PtBr(η1-CH2 C≡CPh) each lead to tautomerization of η1-CH2C≡CPh to η1-C(Ph)=C=CH2, with trans-(PPh3)2PtBr(η1-CH2 C≡CPh) affording [(PMe3)3Pt(η1-C(Ph)=C=CH2)] + at ambient temperature and the slower reacting cis isomer giving [trans-(PPh3)(PMe3)2Pt(η1- C(Ph)=C=CH2)]+ at 54°C . All new complexes were characterized by a combination of elemental analysis, FAB mas spectrometry and IR and NMR (1H, 13C{1H} and 31P{1H}) spectroscopy. The structure of [(PMe3)3Pt(η1-C(Ph)=C=CH2)] BPh4·0.5MeOH was determined by single-crystal X-ray diffraction analysis.
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