16027-45-5Relevant articles and documents
Decomplexation of phosphirane and phosphirene complexes
Van Assema, Sander G. A.,De Kanter, Frans J. J.,Schakel, Marius,Lammertsma, Koop
, p. 5286 - 5291 (2008/10/09)
Novel transient phosphinidene complex Ph-P=Mo(CO)4PMe 3, generated from a 7-phosphanorbornadiene precursor, adds to C=C and C≡C bonds to give Mo(CO)4PMe3-complexed phosphiranes and phosphirenes. The cis-PMe3 ligand weakens the interaction between the molybdenum complex and the three-membered ring. Under mild CO pressure the Mo(CO)4PMe3 transition metal group detaches from the phosphorus center of the ring structure by selective CO substitution. The resulting byproduct Mo(CO)5PMe3 can be reused in the synthesis of the phosphinidene precursor.
Heat of reaction of (norbornadiene)molybdenum tetracarbonyl with monodentate and bidentate ligands. Solution thermochemical study of ligand substitution in the complexes cis-L2Mo(CO)4
Mukerjee, Shakti L.,Nolan, Steven P.,Hoff, Carl D.,Lopez De La Vega, Ramon
, p. 81 - 85 (2008/10/08)
The enthalpy of reaction of (NBD)Mo(CO)4 (NBD = norbornadiene) with a number of monodentate and bidentate ligands forming cis-L2Mo(CO)4 has been measured at 30°C in THF solution. The heats of reaction span a range of 33 kcal/mol. The order of stability for monodentate ligands is PCl3 6H5)3 6H5)3 3 6H5)3 6H5)2(CH3) 6H5)(CH3)2 3)3 3 6H11)NC 3 3. The series of chelating bidentate phosphines R2P-(CH2)nPR2 (n = 1-4, R = C6H5; n = 1, 2, R = CH3) and several related ligands were investigated. The chelating ring systems in the metallacycles show strain energies of about 8 kcal/mol for four-membered rings. The mixed ligand (C6H5)2PCH2CH2-As(C 6H5)2 shows a heat of binding midway between the heats of binding of (C6H5)2PCH2CH2P(C 6H5)2 and (C6H5)2AsCH2C-H2As(C 6H5)2, implying group additivity in this system. The complex (phen)Mo(CO)4 is some 5 kcal/mol more stable than (bpy)Mo(CO)4, presumably due to conformational effects in the free ligand. The ligand 1,5-cyclooctadiene forms a complex 2 kcal/mol less stable than that of norbornadiene. The influences of steric and electronic factors in determining the Mo-L bond strength are discussed.
