Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Carbonylmetal Anions Containing Cyclopentadienyl, PPh3, and NO Ligands. A Route to Dimetal Bridging Carbyne Complexes

Abstract

The reactions of cationic carbyne complexes of manganese and rhenium, [η-C5H5(CO)2M⋮CC6H5]BBr4 (1, M = Mn; 2, M = Re), with Na[η-C5H5Mo(CO)3] (3) in THF at low temperature afford η1,η2-ketene complexes [MnMo{C(CO)C6H5}(CO)4(η-C5H5)2] (8) and [ReMo{C(CO)C6H5}(CO)4(η-C5H5)2] (9), respectively. Analogous reactions of Na[η-C5H5W(CO)3] (4) with 1 and 2 give the corresponding ketene complexes [MnW{C(CO)C6H5}(CO)4(η-C5H5)2] (10) and [ReW{C(CO)C6H5}(CO)4(η-C5H5)2] (11). Na[Co(CO)3PPh3] (5) also reacts with 1 and 2 to yield ketenyl-bridged complexes [MnCo{C(CO)C6H5}(CO)4(PPh3)(η-C5H5)] (12) and [ReCo{C(CO)C6H5}(CO)4(PPh3)(η-C5H5)] (13), respectively. However, compound Na[η-C5H5Fe(CO)2] (6) reacts only with 2 to form a η1,η2-ketene complex [ReFe{C(CO)C6H5}(CO)3(η-C5H5)2] (14), while the reactions of (Ph3P)2N[Fe(CO)3NO] (7) with 1 and 2 produce dimetal bridging carbyne complexes [MnFe(μ-CC6H5)(CO)4(NO)(η-C5H5)] (15) and [ReFe(μ-CC6H5)(CO)4(NO)(η-C5H5)] (16), respectively. Compound 15 treated with an excess of Fe2(CO...