Metal–metal bond cleavage of carbene complexes by halogens: The crystal and molecular structures of ax-[Mn 2(CO) 9{C(OEt)2-thienyl}], [Mn(CO) 4(I){C(OEt)2-thienyl}] and eq-[Mn 2(CO) 9{C(NH 2)2-thienyl}]

• Published in: Journal of organometallic chemistry Vol. 690; no. 24; pp. 5929 - 5937
• Main Authors: Lotz, Simon, Landman, Marilé, Bezuidenhout, Daniela I., Olivier, Andrew J., Liles, David C., van Rooyen, Petrus H.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.12.2005
• Subjects: Carbene complexes; Manganese; Metal carbonyls; Rhenium; Thiophene derivatives; Thiophene derivatives; Carbene complexes; Metal carbonyls; Rhenium; Manganese
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2005.07.090

The metal–metal bond in [M 2(CO) 9{C(OEt)R}] (M = Mn, Re, R = 2-thienyl, 2-bithienyl) is readily cleaved with halogens to afford cis-[M(CO) 4(X){C(OEt)R}] (M = Mn, X = I; M = Re, X = Br). In the binuclear manganese complex, the carbene ligand is found in an axial position, whereas the electronically favoured equatorial position is found for the carbene ligands in the corresponding rhenium complex. The metal–metal bond in [M 2(CO) 9{C(OEt)R}] (M = Mn ( 1), Re ( 2), R = 2-thienyl ( a), 2-bithienyl ( b)) is readily cleaved with halogens to afford cis-[M(CO) 4(X){C(OEt)R}] (M = Mn ( 3), X = I; M = Re ( 4), X = Br). In the binuclear manganese complex, the carbene ligand is found in an axial position due to steric reasons, whereas the electronically favoured equatorial position is found for the carbene ligands in the corresponding rhenium complexes and in [Mn 2(CO) 9{C(NH 2)thienyl}] ( 5a), containing a sterically less demanding NH 2-substituent.