185225-64-3Relevant academic research and scientific papers
Syntheses and chemistry of the diynyl complexes M(C≡CC≡CH)(CO)3(η-C5H5) (M = Mo, W): Crystal structures of W(C≡CC≡CSiMe3)(CO)3(η-C5H 5), W{C≡CC[CH=C(CN)2]=C(CN)2}(CO) 3(η-C5H5)
Bruce, Michael I.,Ke, Mingzhe,Low, Paul J.,Skelton, Brian W.,White, Allan H.
, p. 3539 - 3549 (1998)
Reactions of buta-1,3-diyne with appropriate metal halides, carried out in the presence of CuI in NHEt2, have given high yields of M(C≡CC≡CH)(CO)nCp [M = W (1-W), Mo (1-Mo), n = 3; M = Fe, n = 2 (2)]. Complex 1-W was metalated with LiNPri2; subsequent reactions with SiClMe3 or PClPh2 gave W(C≡CC≡CR)(CO)3Cp [R = SiMe3 (3) or P(O)Ph2 (4)] in modest to high yield. Coupling of 1 with iodoarenes, catalyzed by a mixed CuI-Pd0 catalyst, gave M(C≡CC≡CAr) (CO)3Cp [M = W, Ar = Ph (5-W), tol (6), C6H4OMe-4 (7), C6H4CO2Me-4 (8); M = Mo, Ar = Ph (5-Mo)]. Oxidative coupling of 1 (CuCl-tmed-O2) gave {M(CO)3Cp}2(μ-C8) [M = W (9-W), Mo (9-Mo)]. Addition of tetracyanoethene to 1-W occurred at the C≡C triple bond further from the metal atom, to give W{C≡CC[=C(CN)2]CH=C(CN)2}(CO)3Cp (10). Substitution of CO by PPh3 was difficult, but the Me3NO-induced reaction with 5-W afforded cis-W(C≡CC≡CPh)(CO)2(PPh3)Cp (11) in low yield. The X-ray crystal structures of 3 and 10, together with that of cis-W(C≡CPh)(CO)2(PPh3)Cp (12), are reported.
Syntheses of metal diynyl complexes: Novel routes to all-carbon ligands
Bruce, Michael I.,Ke, Mingzhe,Low, Paul J.
, p. 2405 - 2406 (2007/10/03)
CuI-catalysed reactions between halide complexes of Fe, Mo, W or Pt and an excess of buta-1,3-diyne in the presence of diethylamine lead to the formation of buta-1,3-diynyl compounds; elaboration of the diynyl ligand is achieved by replacement of H by eit
