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Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes:  Reactions of WCl_2(O)(PX_3) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene

de la Mata, F. Javier and Grubbs, Robert H. (1996) Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes:  Reactions of WCl_2(O)(PX_3) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene. Organometallics, 15 (2). pp. 577-584. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20180518-164643556

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Abstract

Complexes of the type WCl_2(O)[PX_3]_3 (PX_3 = P(OMe)_3 (1); PMePh_2 (2)) were synthesized according to procedures previously described in the literature. Upon treatment with 3,3-diphenylcyclopropene, complexes 1 and 2 afforded the corresponding η^2-cyclopropene complexes. Spectroscopic data of W(η^2-diphenylcyclopropene)Cl_2(O)[PX_3]_2 (PX_3 = P(OMe)_3 (4); PMePh_2 (5)) were consistent with an octahedral geometry in which the two mutually trans PX_3 ligands and the cyclopropene ligand occupy equatorial positions cis to the apical oxo ligand. The thermal rearrangement of the η^2-cyclopropene complexes leads to the dimerization product of 3,3-diphenylcyclopropene:  1,1,6,6-tetraphenyl-1,3,5-hexatriene. The presence of carbene species before the dimerization occurs has been demonstrated. Upon treatment with 2 equiv of lithium hexafluoro-tert-butoxide, complexes 4 and 5 give the vinyl alkylidene complexes W(=CHCH=CPh_2)(O)[OC(CH_3)(CF_3)_2]_2[PX_3] (PX_3 = P(OMe)_3 (10); PMePh_2 (7)). The spectroscopic data of 10 and 7 indicated a distorted trigonal bipyramid, where the oxo and alkylidene ligands are cis to each other and placed in the equatorial plane.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/om950389cDOIArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Alternate Title:Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes:  Reactions of WCl2(O)(PX3) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene
Additional Information:© 1996 American Chemical Society. Received May 25, 1995. We gratefully acknowledge support from the NSF, and F.J.M. thanks the Ministerio de Educacion y Ciencia of Spain for a postdoctoral fellowship. Thanks also to Dr. Scott Miller and Jerome P. Claverie for helpful discussions.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Ministerio de Educación y Ciencia (MEC)UNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Division of Chemistry and Chemical Engineering9099
Issue or Number:2
Record Number:CaltechAUTHORS:20180518-164643556
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180518-164643556
Official Citation:Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes:  Reactions of WCl2(O)(PX3) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene F. Javier de la Mata and Robert H. Grubbs Organometallics 1996 15 (2), 577-584 DOI: 10.1021/om950389c
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86484
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:21 May 2018 16:50
Last Modified:03 Oct 2019 19:44

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