title: Binuclear biscarbene complexes of furan.
abstract: Carbene complexes of chromium and tungsten with a bridging furan substituent were synthesized from lithiated furan precursors and metal hexacarbonyls. The binuclear biscarbene complexes [(CO)5M{C(OEt)-C4H2O-C(OEt)}M'(CO)5](M = M'= Cr (3), W (4)) were obtained as well as the corresponding monocarbene complexes [M{C(OEt)-C(4)H3O}(CO)5](M = Cr (1), W (2)). A method of protecting the carbene moiety during the metal acylate stage was used to increase not only the yields of the binuclear Fischer biscarbene complexes 3 and 4 but to establish a method to synthesize analogous mixed heterobinuclear carbene complexes (M = W, M'= Cr (5)) in high yields. The binuclear biscarbene complexes 3 and 5 were reacted with 3-hexyne and yielded the corresponding benzannulated monocarbene complexes [M{C(OEt)-C14H17O3}(CO)5](M = Cr (6), W(7)). Complex 5 reacted regioselectively with the benzannulation reaction occurring at the chromium-carbene centre. The major products from refluxing 3 in the presence of [Pd(PPh3)4] were a monocarbene-ester complex [Cr{C(OEt)-C4H2O-C(O)OEt}(CO)5](8), the 2,5-diester of furan (9) and a carbene-carbene coupled olefin EtOC(O)-C4H2O-C(OEt)=C(OEt)-C4H2O-C(O)OEt (10). X-Ray structure analysis of 4 and 6 confirmed the molecular structures of the compounds in the solid state and aspects of electron conjugation between the transition metals and the furan substituents in the carbene ligands were investigated.
authors.affiliation: Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa.
authors.forename: Chantelle
authors.initials: C
authors.lastname: Crause
authors.forename: Helmar
authors.initials: H
authors.lastname: Görls
authors.forename: Simon
authors.initials: S
authors.lastname: Lotz