Fischer dinuclear and mononuclear bis-carbene complexes of thiophene and thiophene derivatives

The reaction of dilithiated thiophene and thiophene derivatives with group 6 transition metal carbonyl precursors and subsequent alkylation afforded linearly arranged Fischer 2,5-bis-carbene and the rare unsymmetrical 2,3-bis-carbene chelated complexes. The latter requires a second lithiation to occur at an adjacent, less reactive site on the thiophene ring. The control of reactivity sites was investigated and achieved by either blocking more reactive positions with substituents or activating less reactive positions by lithium−halogen exchange reactions. A series of Fischer bis-carbene chelates were synthesized by manipulating the above variables. Structural features of Fischer mono-carbene, mononuclear bis-carbene, and bis-carbene chelated complexes were studied by IR, NMR, and single-crystal X-ray diffractionThe National Research Foundation of South Africa under Grant No. 73679 (S.L.)http://pubs.acs.org/journal/orgnd7hb2017ChemistryChurch History and Church PolicyCivil EngineeringClinical Epidemiolog

Fischer Dinuclear and Mononuclear Bis-Carbene Complexes of Thiophene and Thiophene Derivatives

The reaction of dilithiated thiophene and thiophene derivatives with group 6 transition metal carbonyl precursors and subsequent alkylation afforded linearly arranged Fischer 2,5-bis-carbene and the rare unsymmetrical 2,3-bis-carbene chelated complexes. The latter requires a second lithiation to occur at an adjacent, less reactive site on the thiophene ring. The control of reactivity sites was investigated and achieved by either blocking more reactive positions with substituents or activating less reactive positions by lithium–halogen exchange reactions. A series of Fischer bis-carbene chelates were synthesized by manipulating the above variables. Structural features of Fischer mono-carbene, mononuclear bis-carbene, and bis-carbene chelated complexes were studied by IR, NMR, and single-crystal X-ray diffraction