Novel Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Polymetal Carbonyl Anions. An Approach to Trimetal Bridging Carbyne Complexes

Abstract

The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2Mn⋮CC6H5]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-CC6H5)(CO)6(η-C5H5)] (7). A cationic carbyne complex of rhenium, [(η-C5H5)(CO)2Re⋮CC6H5]BBr4 (2), reacts similarly with 3, affording the corresponding bridging carbyne complex [ReRu2(μ-H)(μ-CO)2(μ3-CC6H5)(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-CC6H5)(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(μ3-CC6H5)(CO)6(η-C5H5)] (12) and [ReFe2(μ-H)(μ-CO)2(μ3-CC6H5)(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-CC6H5)(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 [(η-C5H5)(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.

Acceptor Behavior and E–H Bond Activation Processes of the Unsaturated Heterometallic Anion [MoReCp(μ-PCy2)(CO)5]−(Mo═Re)

“…0.07 Å). Although no related MoRe complexes appear to have been structurally characterized so far (so direct comparisons are not possible), we note that in different MoMn complexes of type [MoMnCp(-SR)(-SR')(CO)5] related to 6, 19…”

Unusual Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with the Carbonylmetal Anions [Ir(CO)4]-and [Ru(CO)4]2-. Novel Route to Heteropolymetallic Bridging Carbyne Complexes

“…In recent years, several new routes to di- and trimetal bridging carbene and carbyne complexes, which were carried out by the reactions of the cationic metal carbyne complexes with metal carbonyl anions, have been developed in our laboratory. One of the synthetic methods for trimetal bridging carbyne complexes is to conduct reactions , of highly electrophilic cationic carbyne complexes of manganese and rhenium, [(η 5 -C 5 H 5 )(CO) 2 M⋮CC 6 H 5 ]BBr 4 ( 1 , M = Mn; 2 , M = Re), with di- or polymetal carbonyl anions of group VIII such as [Fe 2 (μ-CO)(μ-SeC 4 H 9 - n )(CO) 6 ] - , [M 3 (CO) 11 ] 2- (M = Ru, Os), and [Fe 4 (CO) 13 ] - . Recently, in a communication we reported an unusual approach to polymetallic bridging carbyne complexes: the reactions of cationic carbyne complexes of manganese and rhenium, 1 and 2 , with the monoanionic metal carbonyl compound [(Ph 3 P) 2 N][Rh(CO) 4 ] gave novel heteronuclear polymetal clusters with μ and a μ 3 bridging carbyne ligands, A and B , and the related polymetal cluster compound C or D (eq 1).…”

The chemistry of the carbon–transition metal double and triple bond: annual survey covering the year 2002

“…923, Scheme 101) to manganese-and rhenium-carbyne complexes (e.g. 922) was investigated [646]. Formation of heterotrimetallic compounds (e.g.…”