Chelated Fischer carbene complexes of annulated thiophenes: synthesis, structure and electrochemistry. Issue 43 (30th October 2020)

• Record Type: Journal Article
• Authors: Lamprecht, Zandria; Malan, Frederick P.; Fernández, Israel; Lotz, Simon; Bezuidenhout, Daniela I.
• Is Part Of: Dalton transactions. Volume 49:Issue 43(2020)
• Page Start: 15339
• Page End: 15354
• Publication Date: 2020-10-30
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt03298k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The effect of curved or linear band annulated thiophene structures of chelated carbene complexes on conjugation pathways and electronic properties. Abstract : Two (thieno[3, 2- b ]thiophene) and three annulated thiophenes (dithieno[2, 3- b ;3′, 2′- d ]thiophene and dithieno[3, 2- b ;2′, 3′- d ]thiophene) were employed as building blocks to synthesize linear or semi-circular chelated mononuclear biscarbene and dinuclear tetracarbene complexes. The electronic properties of the annulated thienylene chelated carbene complexes were investigated by cyclic voltammetry experiments and compared to non-chelated Fischer-type monocarbene complexes. Density functional theory (DFT) calculations were used to assign the redox events and to probe the extent of electron delocalisation as well as the possibility of electronic (intramolecular metal–metal) communication as a result of intervalence. The differences of these electronic properties in the conjugated chelated carbene complexes are compared to chelated carbene compounds without a linear conjugated pathway.