42847-16-5Relevant academic research and scientific papers
Coupling of acetylenes held proximate to a metal: Alkyne-alkyne interactions in cis-phosphinoacetylene complexes, including structural characterization of the unsymmetrical diphosphine 1-phenyl-2,3-bis(diphenylphosphino)naphthalene and three platinum(II) complexes of Ph2PC≡CPh
Johnson, David K.,Rukachaisirikul, Thitima,Sun, Yan,Taylor, Nicholas J.,Canty, Allan J.,Carty, Arthur J.
, p. 5544 - 5552 (2008/10/08)
The diphenyl(phenylethynyl)phosphine complexes cis-PtX(Y)(Ph2PC≡CPh)2 [X = Y = Cl, I, CF3, C6F5, Me; X (Y) = o-C6H4O2, Me(Cl)] have been synthesized, and for all of the complexes except the dimethyl complex, intramolecular coupling of the phosphinoacetylene ligands occurs on heating to form cis-PtX(Y){o-C16H10(PPh2)2}. A mixture of the two possible structural isomers is formed for cis-PtMe(Cl){o-C16H10(PPh2)2}. The complex cis-PtMe2{o-C16H10(PPh2) 2} has been obtained by reaction of the dichloro analogue with methyllithium. The unsymmetrical diphosphine 1-phenyl-2,3-bis(diphenylphosphino)naphthalene [o-C16H10(PPh2)2], produced as a coordinated ligand via these intramolecular coupling reactions, has been isolated in moderate yield from the dichloro complex and its structure determined by X-ray diffraction. Crystals of o-C16H10(PPh2)2 are triclinic, space group P1, with a = 11.437(13) ?, b = 9.628(12) ?, c = 16.712(21) ?, α = 82.31(9)°, β = 119.08(3)°, γ = 110.03(5)°, and Z = 2. The structure was solved and refined to R = 0.058, Rw = 0.070. Structure determinations of cis-PtCl2(Ph2PC=CPh)2·2MeCN, cis-PtMe(Cl)(Ph2PC=CPh)2·0.5CH2Cl2, and cis-PtMe2(Ph2PC≡CPh)2 have been carried out to evaluate interligand interactions in the complexes. Crystallographic data: cis-PtCl2(Ph2-PC≡CPh)2·2MeCN, monoclinic, space group P21/c, a = 11.604(2) ?, b = 18.416(5) ?, c = 19.344(3) ?, β = 98.63°, Z = 4, R = 0.031, Rw = 0.035; cis-PtMe(Cl)(Ph2PC≡CPh)2·0.5CH 2Cl2, orthorhombic, space group Pbca, a = 16.910(2) ?, b = 17.207(1) ?, c = 25.300(2) ?, Z = 8, R = 0.039, Rw = 0.044; cis-PtMe2(Ph2PC≡CPh)2, orthorhombic, space group Pbca, a = 11.934(2) ?, b = 16.885(3) ?, c = 34.098(8) ?, Z = 8, R = 0.037, Rw = 0.042. Factors affecting the occurrence of intramolecular coupling are assessed, together with a comparison of this reaction with related reactions of organic diacetylenes. The complex cis-PtMe(Cl)(Ph2PC≡CPh)2 reacts with diphenylphosphine to form a mixture of the two structural isomers of cis-PtMe(Cl){Ph2PCH=C(Ph)PPh2}.
