111159-35-4Relevant academic research and scientific papers
Reactions of transition-metal σ-acetylides. 11. Cycloaddition reactions with 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of W{C=CPhC(CF3)2C(CN)2}(CO) 3(η-C5H5), Mn{C=CPhC(CF3)2C(CN)2}(CO)3(dppe), and Fe{C=CPhC(CF3) ...
Bruce, Michael I.,Liddell, Michael J.,Snow, Michael R.,Tiekink, Edward R. T.
, p. 343 - 350 (2008/10/08)
Full title: Reactions of transition-metal σ-acetylides. 11. Cycloaddition reactions with 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of W{C=CPhC(CF3)2C(CN)2}(CO) 3(η-C5H5), Mn{C=CPhC(CF3)2C(CN)2}(CO)3(dppe), and Fe{C=CPhC(CF3)2C(CN)2}(CO) 2(η-C5H5) and of a hydration product, W{NH=C(OH)C(CN)=CCPh=C(CF3)2}(CO)2(η-C 5H5)·H2O. Reactions between W(C2Ph)(CO)3(η-C5H5) (6), Mn(C2Ph)(CO)3(dppe) (7), or Fe(C2Ph)(CO)2(η-C5H5) (8) and (CF3)2C=C(CN)2 give the corresponding σ-cyclobutenyl complexes, all of which have been fully characterized by X-ray crystallography. The butadienyl complex Ni{C[=C(CN)2]CPh=C(CF3)2}(PPh 3)(η-C5H5) (11) was obtained from Ni(C2Ph)(PPh3)(η-C5H5) and the cyanofluoro olefin. Heating 6 in refluxing xylene resulted in ring opening to give W{C[=C(CN)2]CPh=C(CF3)2}(CO) 3(η-C5H5) (9) and the related allyl complex W{η3-C(CF3)2CPhC=C(CN) 2}(CO)2(η-C5H5) (10). Attempts to prepare 10 by reaction of 6 with Me3NO gave instead W{NH=C(OH)C(CN)=CCPh=C(CF3)2}(CO)2(η-C 5H5) (12), confirmed by an X-ray study and formed by addition of H2O to one of the CN groups, followed by chelation. Crystal data for 6: monoclinic, space group Pn, a = 9.575 (2) A?, b = 7.493 (2) A?, c = 15.670 (4) A?, β = 103.79 (2)°, Z = 2; 2641 data were refined to R = 0.075, Rw = 0.079. Crystal data for 7: orthorhombic, space group P212121, a = 11.251 (2) A?, b = 17.888 (3) A?, c = 19.894 (3) A?, Z = 4; 2947 data were refined to R = 0.047, Rw = 0.050. Crystal data for 8: monoclinic, space group P21/a, a = 11.430 (3) A?, b = 15.201 (3) A?, c = 11.887 (2) A?, β = 102.50 (2)°, Z = 4; 2756 data were refined to R = 0.044. Crystal data for 12: monoclinic, space group C2/c, a = 16.089 (3) A?, b = 10.003 (2) A?, c = 32.569 (5) A?, β = 104.2 (1)°, Z = 8; 2433 data were refined to R = 0.042, Rw = 0.047.
