A New Cyclometalation Motif: Synthesis, Characterization, Structures, and Reactivity of Pallada- and Platinacycles with a Bidentate {C(sp(2),cyrhetrene),N}(-) Ligand

作者：Cautivo Teresa; Klahn Hugo^*; Godoy Fernando; Lopez Concepcion; Font Bardia Merce; Calvet Teresa; Gutierrez Puebla Enrique; Monge Angeles

来源：Organometallics, 2011, 30(21): 5578-5589.

DOI：10.1021/om200310r

The synthesis, characterization, X-ray crystal structure, and study of the reactivity of the novel cyretrenyl ligand [{(eta(5)-C5H4-2-C5H4N)}Re(CO)(3) (1) with Pd(OAc)(2) or [MCl2(DMSO)(2)] (M = Pd, Pt) are reported. These studies have allowed us to obtain the bis-mu-ligand cyclopalladated complexes [Pd{[K-2-C,N-(eta(5)-C5H3)-2(C5H4N)]Re(CO)(3))}(mu-X)](2) (X = OAc (2a), CI (4a)) and monomeric pallada- and platinacycles of the general formula [M{[k(2)-C,N-(eta(5)-C5H3)-2(C5H4N)}Re(CO)(3)}(X)(L)] (M = Pd, L = PPh3, X = OAc (3a), Cl (5a); M = Pd, L = DMSO, X = Cl (6a); M = Pt, X = Cl, L = PPh3 (5b), DMSO (6b)), where compound 1 acts as a {C(sp(2),cyrhetrene),N}(-) bidentate ligand. All complexes were characterized by elemental analyses, infrared spectroscopy, and one- and two-dimensional NMR. The X-ray crystal structures of 5a center dot 1/2 CH2Cl2, 5b, 6a center dot CH2Cl2, and 6b confirm (a) the existence of the five-membered metallacycle, (b) the {C(sp(2),cyrhetrene),N}(-) mode of binding of the metallo ligand 1, and (c) the cis arrangement between the metalated carbon and the neutral L ligands (PPh3 or DMSO) in these products. A comparative study of the structures, spectroscopic properties, and reactivities of the new cyclometalated compounds and those of their analogues with a bidentate {C(sp(2),ferrocene),N}(-) ligand is also reported.

• 出版日期2011-11-14