112172-87-9

Upstream product

• 591-51-5 phenyllithium 
• 109-99-9 tetrahydrofuran 
• 17685-52-8 triiron dodecarbonyl 
• 302352-26-7 [Fe2(μ-CO)(μ-CC6H5)(CO)2(η-C5H5)2][BBr4] 
• 108-98-5 thiophenol 
• 25879-01-0 Et₄N{HFe(CO)4} 
• 106-45-6 para-thiocresol 
• 14040-11-0 tungsten hexacarbonyl 

Relevant academic research and scientific papers

Reactions of nucleophiles with cationic bridging alkylidyne complexes

The reaction of the μ-methylidyne complex 2(μ-CH)>+ PF6- (1) with C6H5(CH3)2SiLi and CuI produced 2(μ-CO) (4).Reaction of p-totyl carbyne complex 2(μ-CO)(μ-CC6H4-p-CH3)>+ B

Unusual reactions of cationic bridging carbyne complexes of bis(η5-cyclopentadienyl)diiron tricarbonyl with carbonylmetal anions. A route to diiron bridging carbyne complexes

The reactions of cationic carbyne complexes of diiron, [Fe2(μ-CO)(μ-CPh)(CO)2 (η5-C5H5)2]-BBr4 (1), with the anionic carbonylmetal compounds Na[M (CO)5CN] (3, M = Cr; 4, M = Mo; 5, M = W) in THF at low temperature afford the novel bridging carbyne complexes [Fe2(μ-CO)(μ-CPh)(CO)2 (η5-C5H5)2NCM(CO)5] (6, M = Cr; 7, M = Mo; 8, M = W). In contrast to the reaction of 1, the cationic carbyne complex [Fe2(μ-CO)(μ-CC6H4Me-p)(CO)2(η5-C5 H5)2]BBr4 (2) reacts with carbonylmetal anions 3-5 under the same conditions to produce the novel bridging p-tolyl(pentacarbonylcyanotungsten)carbene complexes [Fe2(μ-CO) {μ-C(C6H4Me-p)(CO)2(η5-C5H5)2 NCM(CO)5}] (9, M = Cr; 10, M = Mo; 11, M = W). However, the analogous reaction of Na[Fe(CO)4CN] with 1 yields the diiron bridging phenylcarbene complex [Fe2(μ-CO){μ- C(H)Ph}(CO)2(η5-C5H5)2] (12). The structures of 7, 8, and 11 have been established by X-ray crystallography.

Reactions of cationic bridging carbyne complexes of bis(η-cyclopentadienyl)diiron tricarbonyl with nucleophiles. A route to diiron bridging carbene complexes

The reactions of the cationic carbyne complex of diiron, [Fe2(μ-CO)(μ-CPh)(CO)2(η-C5H5) 2]- BBr4 (3), with NaSMe, NaSEt, NaSPh, NaSC6H4Me-p, and NaSC6H4NO2-p in THF at low temperature afforded diiron bridging thiocarbene complexes [Fe2(μ-CO){μ-C(SR) Ph}(CO)2-(η-C5H5)2] (5, R = Me; 6, R = Et; 7, R = Ph; 8, R = p-MeC6H4; 9, R = p-NO2C6H4). Complex [Fe2(μ-CO)(μ-CC6 H4Me-p)(CO)2(η-C5H5)2]BBr4 (4) reacted similarly with NaSPh and NaSC6H4-Me-p to give corresponding bridging carbene complexes [Fe2(μ-CO){μ-C(SR)C6 H4Me-p}(CO)2-(η-C5H5)2] (10, R = Ph; 11, R = p-MeC6H4). Complex 3 also reacted with NaOPh and NaN(SiMe3)2 to yield bridging carbene complexes [Fe2(μ-CO){μ-C(OPh)Ph}(CO)2(η- C5 H5)2] (12) and [Fe2(μ-CO){μ- C(N(SiMe3)2)Ph}(CO)2(η-C5H5) 2] (13), respectively. Complexes 3 and 4 reacted with reactive salt [Et3NH][Fe2(μ-CO)(μ-SBun)(CO)6 ] to yield the bridging mercaptocarbene complex [Fe2(μ-CO) {μ-C(SH)Ph}(CO)2(η-C5H5)2] (14) and the bridging butylthiocarbene complex [Fe2(μ-CO){μ-C(SBun)C6H4 Me-p}(CO)2(η-C5H5)2] (15), respectively. The analogous reactions of [Et3NH][Fe2(μ-CO) (μ-SPh)(CO)6] with 3 and 4 afforded the thiolato-bridge iron carbonyl compound [Fe2(μ-SPh)2(CO)6] (16) and the bridging arylcarbene complexes [Fe2(μ-CO){μ-C(H)Ar}(CO)2(η-C$ -5$/ H5)2] (17, Ar = Ph; 18, Ar = p-MeC6H4), while [Et3NH][Fe2(μ-CO)(μ-SC6H4Me-p) (CO)6] reacted with 3 to yield 17 and [Fe2(μ-SC6H4Me-p)2-(CO)6] (19). The reaction of metal carbonyl anion compounds Na2W(CO)5 and Na2Fe(CO)4 with 3 gave the same product, 17. The structures of 6, 7, 15, and 17 have been established by X-ray diffraction studies.

The μ-sulfonium-methylidene diiron complexes [Fe2(μ-C(X)SMe2)(μ-CO)(CO)2(Cp) 2]SO3CF3 (X=CN, H) as precursors of μ-alkylidene complexes

The reactions of [Fe2(μ-C(X)SMe2)(μ-CO)(CO)2(Cp) 2]SO3CF3 (X=CN 2a, H 2b; Cp=η-C5H5) with Li2Cu(CN)R2 (R=Me, Bun, Ph, CCC6H4Me-4, C4H3S) give the neutral μ-alkylidene complexes [Fe2(μ-C(X)R)(μ-CO)(CO)2(Cp)2] (3) arising from nucleophilic attack at the bridging carbon and SMe2 displacement. Likewise, 2a,b react with the sodium salt of dimethylmalonate, diethylmalonate, ethylacetoacetate, 2,4-pentanedione, dibenzoylmethane and benzylcyanide, resulting in the formation of the corresponding functionalized μ-alkylidene complexes [Fe2(μ-C(X)R)(μ-CO)(CO)2(Cp)2] (5-7) (X=CN, H; R=CH(COOMe)2, CH(COOEt)2, CH(COOMe)(COMe), CH(COMe)2, CH(COPh)2, CH(Ph)CN). The dichetone adducts [Fe2(μ-C(X)CH(COR)2)(μ-CO)(CO)2(Cp) 2] (X=CN, H; R=Me, Ph) undergo deacylation upon treatment with alumina, leading to the formation of the complexes [Fe2(μ-C(X)CH2C(O)R)(μ-CO)(CO)2(Cp) 2]. Reactions of 2a,b with LiBu or PhLi result in the formation the metallacycles [Fe2(μ-C(X)S(Me)CH2)(μ-CO)(CO)(CO)(Cp)2] (X=CN, 4a; H 4b) which arise from the deprotonation of an SMe group and the intramolecular addition at a terminally coordinated carbonyl. Finally, a comparison of the reactivity of 2a,b with that of the μ-carbyne diiron complexes [Fe2(μ-CX)(μ-CO)(CO)2(Cp)2]SO 3CF3 (X=H, SMe, NMe2) is presented.

Reactions of heteroatom and carbon nucleophiles with the cationic bridging methylidyne complex {[(C5H5)(CO)Fe]2(μ-CO)(μ-CH)} +PF6-

The reaction of the μ-methylidyne complex {[(C5H5)(CO)Fe]2(μ-CO)(μ-CH)} +PF6- (1) with NMe3 and (C6H5)2C=NH gave the cationic 1:1 adducts {[(C5H5)(CO)Fe]2(μ-CO)(μ-CHNMe 3)}+PF6- (3) and {[(C5H5)(CO)Fe]2(μ-CO)[μ-CHNH=C(C 6H5)2]}+PF6- (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH3)3 gave the neutral μ-carbene complex [(C5H5)(CO)Fe]2(μ-CO)[μ-CHOC(CH 3)3] (4). Reaction of 1 with water afforded a 1:1 mixture of μ-methylene complex [(C5H5)(CO)Fe]2(μ-CO)(μ-CH2) (2) and [(C5H5)(CO)Fe]2(μ-CO)2; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et4N+Br- gave the unstable μ-carbene complex [(C5H5)(CO)Fe]2(μ-CO)(μ-CHBr) (6). Reaction of 1 with the carbon nucleophiles CH3Li and Li(C6H5CuCN) gave the μ-carbene complexes [(C5H5)(CO)Fe]2(μ-CO)(μ-CHCH3) (11) and [(C5H5)(CO)Fe]2(μ-CO)(μ-CHC 6H5) (12), while reaction of 1 with HFe(CO)4- afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral μ-carbene complex [(C5H5)-(CO)Fe]2(μ-CO)(μ-CHCH 2COCH3)] (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar μ-carbene products.