Formation, reactions, and solution dynamics of [M(η1-C5H4R)(C6H4-2-X)(PEt3)2] (M = Pd, Pt)

Anderson, G. K., Black, D. M., Cross, R. J., Robertson, F. J., Rycroft, D. S. and Wat, R. K.M. (1990) Formation, reactions, and solution dynamics of [M(η1-C5H4R)(C6H4-2-X)(PEt3)2] (M = Pd, Pt). Organometallics, 9(9), pp. 2568-2574. (doi:10.1021/om00159a027)

Full text not currently available from Enlighten.

Abstract

Reactions of [M(η5-C5H4R)(C6H4-2-X)] (M = Pd, R = H, Me, SiMe3, X = N=NPh or R = H, X = CH=NMe, 2-C5H4N; M = Pt, R = H, SiMe3, X = N=NPh) with PEt3 in toluene solution produce the adducts [Pd(η5-C5H4R)(C6H4-2-X)(PEt3)] and trans-[M(η1-C5H4R)(C6H4-2-X)(PEt3)2] but none of the ionic [M(C6H4-2-X)(PEt3)3]+C5H4R found in halogenated solvents. Instead, the reactive intermediates cis-[M(η1-C5H4R)(C6H4-2-X)(PEt3)2] are detected at −80 ºC, but these isomerize as the temperature is raised. The fluxional η1-C5H4R groups of trans-[M(η1-C5H4R)(C6H4-2-X)(PEt3)2] undergo rapid rotation about the M–C bonds at ambient temperature, resulting in apparent magnetic equivalence of the PEt3 groups. At temperatures around −90 ºC bond rotation is slowed sufficiently to allow detection of the nonequivalent P atoms by NMR spectroscopy. The palladium complexes decompose slowly at 25 ºC, but the platinum species isomerize readily to sp2-carbon-bonded vinylic cyclopentadienyl derivatives. At low temperatures the effects of restricted rotation about the Pt–C bonds of the vinylic cyclopentadienyl compounds can be deduced from the detection of syn and anti rotational isomers in solution.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Rycroft, Dr David
Authors: Anderson, G. K., Black, D. M., Cross, R. J., Robertson, F. J., Rycroft, D. S., and Wat, R. K.M.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Organometallics
Publisher:American Chemical Society
ISSN:0276-7333
ISSN (Online):1520-6041

University Staff: Request a correction | Enlighten Editors: Update this record