68110-76-9Relevant articles and documents
Reversible formation of η1- and η0-cyclopentadienyl complexes by treatment of [M(C6H4N=NC6H4R)(η 5-C5H5)] (M = Pd, Pt) with tertiary phosphines
Anderson, Gordon K.,Cross, Ronald J.,Fallis, Stephen,Rocamora, Mercè
, p. 1440 - 1446 (2008/10/08)
Reactions of [2-(arylazo)phenyl](η5-cyclopentadienyl)palladium compounds with PEt3 or P-n-Bu3 in CDCl3 or CD2Cl2 solution follow two independent, competing pathways. One route reversibly produces first [Pd(C6H4N=NC6H4R)(η 5-C5H5)(PR′3)] (2) and then trans-[Pd(C6H4N=NC6H4R)(η 1-C5H5)(PR′3)2] (3). The other route, which is favored by lower temperatures and excess PR′3, leads instead to the ionic cyclopentadienyl compound [Pd(C6H4N=NC6H4R)(PR′ 3)3]+C5H5-. At temperatures above -40°C, both the η1- and η0-cyclopentadienyl complexes undergo H-D exchange with CDCl3, deuteriating the Cp rings. At higher temperatures, further irreversible reactions with the chlorinated solvents produce trans-[Pd-(C6H4N=NC6H 4R)Cl(PR′3)2]. Although the platinum complex [Pt(C6H4N=NC6H5)(η 5-C5H5)] reacts in a broadly similar way, [Pt(C6H4N=NC6H5)(η 5-C5H5)(PR′3)] could not be detected in any reaction sequences. The mechanisms involved in the H-D exchange reactions are discussed, and complete assignments of the 1H and 13C{1H} NMR spectra of the (arylazo)phenyl compounds have been made.
