Cationic Carbyne Complexes Of Manganese Research Articles

Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with the Carbonylrhodium Anion [Rh(CO)4]-. A Novel Route to Heteropolymetallic Bridging Carbyne Complexes with μ- and μ3-Carbyne Ligands

The reaction of cationic carbyne complexes of manganese and rhenium, [η5-C5H5(CO)2M⋮CC6H5]BBr4 (1, M = Mn; 2, M = Re), with [(Ph3P)2N][Rh(CO)4] in THF at low temperature gives the novel Mn2−Rh2 mix...

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

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, g...

Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Diiron Anions [Fe2(μ-CO)(μ-SeR)(CO)6]-. A Route to RSe-Bridged Dimetal Bridging Carbene Complexes

The reactions of cationic carbyne complexes of manganese and rhenium, [η-C5H5(CO)2M⋮CC6H5]BBr4 (1, M = Mn; 2, M = Re), with diiron anionic compounds [Et3NH][Fe2(μ-CO)(μ-SeR)(CO)6] (3, R = C6H5; 4, R = p-CH3C6H4) in THF at low temperature gave the dimetal bridging carbene complexes [MFe{μ-C(SeR)C6H5}(CO)5(η-C5H5)] (10, M = Mn, R = C6H5; 11, M = Mn, R = p-CH3C6H4; 13, M = Re, R = C6H5; 14, M = Re, R = p-CH3C6H4), [η-C5H5M(CO)3] (7, M = Mn; 12, M = Re), and [Fe2(μ-SeR)2(CO)6] (8, R = C6H5; 9, R = p-CH3C6H4). Complexes 1 and 2 also react with [MgBr][Fe2(μ-CO)(μ-SeC2H5)(CO)6] (5) to produce [Fe2(μ-SeC2H5)2(CO)6] (15) and dimetal bridging carbene complexes [MnFe{μ-C(SeC2H5)C6H5}(CO)5(η-C5H5)] (17) and [ReFe{μ-C(SeC2H5)C6H5}(CO)5(η-C5H5)] (18), respectively. 2 reacts similarly with [MgBr][Fe2(μ-CO)(μ-SeC4H9-n)(CO)6] (6) to give [Fe2(μ-SeC4H9-n)2(CO)6] (16) and a Re−Fe bridging carbene complex [ReFe{μ-C(SeC4H9-n)C6H5}(CO)5(η-C5H5)] (19), while the analogous reaction of 1 with 6 produced an unexpected trimetal bridging carbyne complex [MnFe2(μ-H)(μ-CO)2(μ3-CC6H5)CO)6(η-C5H5)] (20). The structures of complexes 9, 10, 13, 18, and 20 have been established by X-ray diffraction studies.

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

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...

Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Na[Fe(CO)4CN] and Et4N[Mn(CO)4(CN)2

The reaction of a cationic carbyne complex of manganese, [(η-C5H5)(CO)2Mn⋮CC6H5]BBr4 (1), with Na[Fe(CO)4CN] (3) in THF at low temperature gives the phenyl(tetracarbonylcyanoiron)carbene−manganese complex [(η-C5H5)(CO)2MnC(C6H5)NCFe(CO)4] (5). The analogous reaction of a cationic carbyne complex of rhenium, [(η-C5H5)(CO)2Re⋮CC6H5]BBr4 (2), with 3 affords the corresponding carbene−rhenium complex [(η-C5H5)(CO)2ReC(C6H5)NCFe(CO)4] (6). Complex 1 reacts with Et4N[Mn(CO)4(CN)2] (4) to yield the novel trinuclear metal dicarbene−manganese complex [{(η-C5H5)(CO)2MnC(C6H5)NC}2Mn(CO)3CN] (7) and the novel tetranuclear metal dicarbene−manganese complex [{(η-C5H5)(CO)2MnC(C6H5)NC}2Mn(CO)3CNMn(CO)2(η-C5H5)] (8). Complex 2 reacts similarly with 4 to afford the corresponding trinuclear dicarbene−rhenium complex [{(η-C5H5)(CO)2ReC(C6H5)NC}2Mn(CO)3CN] (9). The structures of complexes 5−9 have been established by X-ray crystallography.

Novel Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with (Ph3P)2NW(CO)5NCO, (Ph3P)2NW(CO)5SCN, and NaW(CO)5CN

The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4 (1), with (Ph3P)2NW(CO)5NCO (3) in THF at low temperature gave the novel chelated carbene complex [η-C5H4(CO)2MnC(NHCO)C6H5] (6). The analogous reaction of a cationic carbyne complex of rhenium, [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2), with 3 afforded the azametallacyclic complex [η-C5H5(CO)2ReC(C6H5)(CO)NW(CO)5] (7). The reaction between 1 and (Ph3P)2NW(CO)5SCN (4) led to the loss of a sulfur atom to give the phenyl(pentacarbonylisocyanotungsten)carbene−manganese complex [η-C5H5(CO)2MnC(C6H5)CNW(CO)5] (8). However, the reaction of 2 with 4 afforded the (isothiocyanato)phenylcarbene−rhenium complex [η-C5H5(CO)2ReC(C6H5)SCN] (9). Complexes 1 and 2 react with NaW(CO)5CN (5) to produce novel phenyl(pentacarbonylcyanotungsten)carbene−manganese and −rhenium complexes, [η-C5H5(CO)2MnC(C6H5)NCW(CO)5] (10) and [η-C5H5(CO)2ReC(C6H5)NCW(CO)5] (11), respectively. The structures of 6, 7, 8, and 11 have been established by X-ray diffraction studies.

Unexpected Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Mixed-Dimetal Carbonyl Anions. A New Route to Dimetal Bridging Carbyne Complexes

The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4 (1), with (Ph3P)2NFeCo(CO)8 (3) in THF at low temperature gave a heteronuclear dimetal bridging carbyne complex [MnCo(μ-CC6H5)(CO)5(η-C5H5)] (5) and a bridging carbene complex [MnCo{μ-C(CO)C6H5}(CO)5(η-C5H5)] (6). Ph3P)2NWCo(CO)9 (4) also reacted with 1 to give the same products 5 and 6. The analogous reaction of the cationic carbyne complex of rhenium, [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2), with 3 or 4 afforded the corresponding bridging carbyne complex [ReCo(μ-CC6H5)(CO)5(η-C5H5)] (7) and bridging carbene complex [ReCo{μ-C(CO)C6H5}(CO)5(η-C5H5)] (8). 5 can convert to 6 by reaction with carbon monoxide gas. 5 or 6 reacted with Fe2(CO)9 to afford a trimetal bridging carbyne complex [MnFeCo(μ3-CC6H5)(μ-CO)(CO)7(η-C5H5)] (9). Analogous reaction of 7 or 8 with Fe2(CO)9 yielded the trimetal bridging carbyne complex [ReFeCo(μ3-CC6H5)(CO)8(η-C5H5)] (10). The structures of 5, 7, 8, 9 and 10 have been established by X-ray diffraction studies.

Unusual Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Reactive Salts [Et3NH][(μ-CO)(μ-RS)Fe2(CO)6]. A Route to Dimetal Bridging Carbene Complexes

The reaction of a cationic carbyne complex of manganese, [η-C5H5(CO)2Mn⋮CC6H5]BBr4 (1), with the reactive salt [Et3NH][(μ-CO)(μ-n-C4H9S)Fe2(CO)6] (3) in THF at low temperature gave the dimetal bridging carbene complex [MnFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (8) and [Fe(CO)3(n-C4H9S)]2 (7). 1 reacted with [Et3NH][(μ-CO)(μ-C6H5S)Fe2(CO)6] (4) to give the bridging carbene complex [MnFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (11) and the manganese phenylthiocarbene complex [η-C5H5(CO)2MnC(C6H5S)C6H5] (12), besides [Fe(CO)3C6H5S]2 (10). 1 also reacted with [Et3NH][(μ-CO)(μ-p-CH3C6H4S)Fe2(CO)6] (5) to yield [Fe(CO)3(p-CH3C6H4S)]2 (13) and the bridging carbene complex [MnFe{μ-C(p-CH3C6H4S)C6H5}(CO)5(η-C5H5)] (14). Analogous reactions of the cationic rhenium carbyne complex [η-C5H5(CO)2Re⋮CC6H5]BBr4 (2) with 3 and 4 gave the corresponding bridging carbene complexes [ReFe{μ-C(n-C4H9S)C6H5}(CO)5(η-C5H5)] (16) and [ReFe{μ-C(C6H5S)C6H5}(CO)5(η-C5H5)] (17) and the phenylthiocarbene complex [η-C5H5(CO)2ReC(C6H5S)C6H5] (18), respectively. The structures of 8, 11, 12, 16, and 18 have been established by X-ray diffraction studies.

Unusual reactions of cationic carbyne complexes of manganese and rhenium with [NMe4][HFe(CO)4] to form heteronuclear dimetal carbene-bridged complexes

The reaction of a cationic carbyne complex of manganese [Mn(CPh)(η-C5H5)(CO)2]BBr4 1 with the salt [NMe4][HFe(CO)4] 3 in thf at low temperature gave [Mn(η-C5H5)(CO)3] 4 and a novel dimetal carbene-bridged complex [MnFe{µ-C(H)Ph}(η-C5H5)(CO)5] 5. The cationic rhenium carbyne complex [Re(CPh)(η-C5H5)(CO)2]BBr4 2 similarly reacted with 3 to give [Re(η-C5H5)(CO)3] 6 and [ReFe{µ-C(H)Ph}(η-C5H5)(CO)6] 7. Complex 5 reacted with carbon monoxide gas leading to cleavage of the µ-C–Mn and Mn–Fe bonds to afford 4 and a novel benzene-co-ordinated acyltricarbonyliron complex [Fe(PhCHCO)(CO)3] 8. The reaction of 7 with PPh3 yielded [ReFe{µ-C(H)Ph}(η-C5H5)(CO)5(PPh3)] 9. The structures of complexes 5, 8 and 9 have been established by X-ray diffraction studies.

Reactions of cationic carbyne complexes of manganese and rhenium with metal carbonyl anions

Treatment of [(η-C5H5)(OC)2MnCC6H5]BBr4 1 and [(η-C5H5)(OC)2ReCC6H5]BBr4 2 with the carbonyl monoanion [Mn(CO)5]– 3 in THF at low temperature afforded the ketenyl bridged complexes [Mn2{µ-C(CO)C6H5}(CO)6(η-C5H5)] 6 and [ReMn{µ-C(CO)C6H5}(CO)6(η-C5H5)] 7 respectively. The analogous reactions of complexes 1 and 2 with [Co(CO)4]– 4 gave corresponding ketenyl bridged complexes [MnCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] 8 and [ReCo{µ-C(CO)C6H5}(CO)5(η-C5H5)] 9 respectively. Complexes 1 and 2 reacted with the carbonyl dianion [W(CO)5]2– 5 to give the dimetal carbene bridged complexes [MnW{µ-C(H)C6H5}(CO)7(η-C5H5)] 10 and [ReW{µ-C(H)C6H5}(CO)7(η-C5H5)] 11 respectively. The structures of complexes 6, 9 and 11 have been established by X-ray diffraction studies.

Unusual reactions of a cationic carbyne complex of manganese with carbonyliron dianions to form a novel dimetal carbene-bridged complex [MnFe{µ-C(COEt)Ph}(η-C5H5)(CO)5

The reaction of [Mn(CPh)(η-C5H5)(CO)2]BBr41 with [NEt4]2[Fe2(CO)8] in tetrahydrofuran at low temperature gave a novel heteronuclear dimetal carbene-bridged complex [MnFe{µ-C(COEt)Ph}(η-C5H5)(CO)5]3, and a dimetal dicarbene complex [{(OC)2(η-C5H5)Mn(CPh)}2Fe2(CO)8]4, as well as [Mn(η-C5H5)-(CO)3]2. The same products, 2 and 3, were obtained from the reaction of 1 with Na2[Fe(CO)4]. The structure of 3 has been established by X-ray crystallography.

Übergangsmetall-carben-komplexe : XCIX. Cyanid und isothiocyanat als substituenten in carben-liganden

The reaction of cationic carbyne complexes of manganese and rhenium with the pseudohalides cyanide and isothiocyanate yields novel carbene complexes. The reaction proceeds by nucleophilic attack of the anions at the carbyne carbon in the cationic complex. The structures of the new complexes are derived from spectroscopic data and elemental analyses.