Molybdenum- and tungsten-cyclopentadienyl carbonyl complexes with hetero-allyl derivatives as ligand
Journal of Organometallic Chemistry(1981)
摘要
The functionally substituted phosphines LH = Ph2PC(X)N(H)R (X = S, R = Ph, Me; X = O, R = Ph; X = N-p-tol, R = p-tol) behave as neutral monodentate (LH) ligands in substitution reactions with M(CO)3(η5-C5H5)Cl (M = Mo, W), forming M(CO)2(η5-C5H5)Cl(LH) with P bonded to the metal atom. Deprotonation under the influence of the base Et3N occurs only in the case of X = S and the chelate complexes M(CO)2(η5-C5H5)(L−) are formed with coordination via P and S. The related ligand Me2NC(S)N(H)R (R = Me, Ph) reacts in the presence of Et3N to form M(CO)2(η5-C5H5)(L−) (M = Mo, W; L− = Me2NC(S)NR−; R Me, Ph) with coordination via S and N. Tetramethyldithiobiuret (Me2NC(S)N(H)C(S)NMe2) reacts with Mo(CO)3(η5-C5H5)Cl only when Et3N is present and a complex with a six-membered ring is formed. The molybdenum complexes were prepared by thermal reactions while the tungsten complexes were also prepared photochemically. The complexes were characterised by means of elemental analysis, infrared spectroscopy, and 1H and 31P[1H] NMR spectroscopy.
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