An η2transition state for the insertion of M(PR3)2fragments (M = Pd or Pt) into the phosphorus–carbon bonds of pentacarbonyl(phosphirane)tungsten complexes
- 1 January 1993
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 1811-1822
- https://doi.org/10.1039/dt9930001811
Abstract
The reaction of (E)- and (Z)-[W(CO)5( [graphic omitted]HPh)] complexes with [M(PR3)2(C2H4)][M = Pd, (PR3)2= dppe (Ph2PCH2CH2PPh2); M = Pt, PR3= PPh3] has been studied and the following products [which result from insertion of the M(PR3)2 frogment into the phosphirane ring] have been fully characterised by NMR spectroscopy: (2R*,3S*,4S*)-(±)-, (2R*,3S*,4R*)-(±)- and (2R*,3S*,4R*)-(±)-[(dppe) Pd(CHPhCHPhPPh)W(CO)5]; (2S*,3S*,4S*)-(±)-, (2S*3R*4R*)-(±)- and (2S*,3S*,4R*)-(±)-[(Ph3P)2Pt(CHPhCHPhPPh)W(CO)5]; and trans-(2S*,3S*,4R*)-(±)-[(Ph3P)(OC)Pt-(CHPhCHPhPPh)W(CO)5]. The crystal and molecular structures of (Z)-[W(CO)5([graphic omitted]HPh)], (2R*,3S*,4R*)-(±)- and (R*,3S*,4S*)-(±)-[(dppe)Pd(CHPhCHPhPPh)W(CO)5] have been determined. The configurations of the products are interpreted in terms of a transition state in which a P–C bond is η2-co-ordinated to M(PR3)2 fragment.Keywords
This publication has 47 references indexed in Scilit:
- Activation of a fluorinated carbon-carbon bond by oxidative addition of tetrafluorocyclopropene to platinum(0). The first example of a perfluorometallacyclobuteneOrganometallics, 1988
- Selective catalytic dehydrogenation of alkanes to alkenesJournal of the American Chemical Society, 1987
- Transition-metal-mediated phosphorus-carbon bond cleavage and its relevance to homogeneous catalyst deactivationChemical Reviews, 1985
- The carbene-like behavior of terminal phosphinidene complexes toward olefins. A new access to the phosphirane ringOrganometallics, 1984
- Synthese und Umlagerungen von 2‐VinylphosphiranenEuropean Journal of Inorganic Chemistry, 1983
- Herstellung von 2-VinylphosphiranenAngewandte Chemie International Edition in English, 1982
- The structure of a metallocyclobutane complex, Pt[C3H2(CN)4][P(C6H5)3]2, the product of the reaction between 1,1,2,2-Tetracyanocyclopropane and Pt[P(C6H5)3]4Journal of Organometallic Chemistry, 1974
- Complexes of PhosphiraneAngewandte Chemie International Edition in English, 1971
- Microwave spectra, molecular structure, and dipole moment of phosphiraneJournal of the American Chemical Society, 1969
- The Reaction of Dipotassium Cyclooctatetraenide with Dichlorophenylphosphine. Rearrangements of 9-Phenyl-9-phosphabicyclo[6.1.0]nonatriene and 9-Phenyl-9-phosphabicyclo[4.2.1]nonatrieneJournal of the American Chemical Society, 1966