202283-38-3Relevant articles and documents
Novel reactions of cationic carbyne complexes of manganese and rhenium with polymetal carbonyl anions. An approach to trimetal bridging carbyne complexes
Xiao, Nu,Xu, Qiang,Tsubota, Susumu,Sun, Jie,Chen, Jiabi
, p. 2764 - 2772 (2008/10/08)
The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2Mn≡CC6H 5]BBr4 (1), with [(Ph3P)2N]2[Ru3(CO)11] (3) in THF at low temperature gave the heteronuclear trimetal bridging carbyne complex [MnRu2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (7). A cationic carbyne complex of rhenium, [(η-C5H5)(CO)2Re≡CC6H 5]BBr4 (2), reacts similarly with 3, affording the corresponding bridging carbyne complex [ReRu2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (8) and neutral Re-carbyne dimer [Re(CO)2(η-C5H5)(μ-CC6H5 )]2 (9). The compound [(Ph3P)2N]2[Os3(CO)11] (4) only reacts with 1 to give the trimetal bridging carbyne complex [MnOs2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (10) and neutral Mn-carbyne dimer [Mn(CO)2(η-C5H5)(μ-CC6H5 )]2 (11). [(Ph3P)2N]2[Fe4(CO)13] (5) also reacts with cationic carbyne complexes 1 and 2 to give the trimetal bridging carbyne complexes [MnFe2(μ-H)(μ-CO)2(μ3CC6H 5)(CO)6(η-C5H5)] (12) and [ReFe2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)6(η-C5H5)] (13), respectively. Product 13, when treated with an excess of PPh3, gave the PPh3-substituted bridging carbyne complex [ReFe2(μ-H)(μ-CO)2(μ3-CC6H 5)(CO)5(PPh3)(η-C5H5) ] (14). In contrast to carbonylmetal anions 3-5, [Mo(η-C5H5)2(H)CO][Mn3(CO)9 (μ-SC6H5)4] (6) reacts with 1 to produce not the analogous bridging carbyne complexes but rather the mercapto-carbene complex [(ηC5H5)(CO)2Mn=C(SC6H5 )C6H5] (15) and the thiolato-bridged Mo-Mn carbonyl complex [Mo(η-C5H5)(CO)2(μ-SC6H5 )2Mn(CO)3] (16), while the analogous reaction of 2 with 6 yields the mercaptocarbene complex [(η-C5H5)(CO)2Re=C(SC6H5 )C6H5] (17) and phenylcarbene complex [(η-C5H5)(CO)2Re=C(H)C6H5 ] (18). The structures of 7, 9, 13, 14, and 16 have been established by X-ray diffraction studies.
