81869-34-3Relevant academic research and scientific papers
REACTIONS BETWEEN TETRACYANOETHYLENE AND TRANSITION METAL ACETYLIDES: FORMATION AND CLEAVAGE OF THE CYCLOBUTENYL RING IN AN AUTHENTIC TETRACYANOCYCLOBUTENYLMETAL COMPLEX,
Bruce, Michael I.,Hambley, Trevor W.,Rodgers, John R.,Snow, Michael R.,Swincer, A. Geoffrey
, p. C1 - C4 (1982)
The reaction between W(CCPh)(CO)3(η-C5H5) and C2(CN)4 affords , which has been characterised by X-ray crystallography; the four-membered ring is cleaved thermally to give WCPh=C(CN)2>(CO)3(η-C5H5), which in turn is converted photoch
Reactions of transition-metal σ-acetylide complexes. 1. The reaction between W(C2Ph)(CO)3(η-C5H5) and tetracyanoethylene: X-ray structure off W(CO)2[η3-C(CN)CPhC=C(CN)2](η-C 5H5)·0.5C2(CN)4
Bruce, Michael I.,Hambley, Trevor W.,Snow, Michael R.,Geoffrey Swincer
, p. 494 - 500 (2008/10/08)
The reaction between W(C2Ph)(CO)3(η-C5H5) and C2(CN)4 gives a relatively long-lived (hours) green paramagnetic compound (nine-line ESR spectrum, g = 1.997). On standing the σ-cyclobutenyl complex W[C=CPhC(CN)2C(CN)2](CO)3(η-C 5H5) is obtained, which is slowly converted to the σ-butadienyl derivative W{C[=C(CN)2]CPh=C(CN)2}(CO)3(η-C 5H5). UV irradiation of the butadienyl complex gives the dicarbonyl W(CO)2[η3-C(CN)2CPhC=C(CN) 2](η-C5H5) in which the cyanocarbon ligand has been shown crystallographically to be best represented either as a methylenetungstabicyclobutane or as a localized en-yl system, probably with substantial back-bonding from the metal to the σ-bonded carbon. Crystals are monoclinic of space group P21/n with a = 12.194 (4) A?, b = 20.858 (5) A?, c = 8.969 (2) A?, β = 98.21 (2)°, and Z = 4; the unit cell also contains two molecules of C2(CN)4. Refinement of 2781 data converged with R = 0.0389 and Rw = 0.0384. The structural data are used to rationalize unusual 13C chemical shifts of the metal-bonded carbon atoms.
