16742-99-7Relevant academic research and scientific papers
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.
Oxygen atom transfer reaction to metal carbonyls. Kinetics and mechanism of CO-substitution reactions of Mo(CO)5L in the presence of (CH3)3NO
Gao, Yi-Ci,Shi, Qi-Zhen,Kershner, David L.,Basolo, Fred
, p. 188 - 191 (2008/10/08)
Kinetic data are reported for the reactions of Mo(CO)5L (where L1 = P(c-Hx)3, P(n-Bu)3, NMe3, py, PPh3, AsPh3, P(OEt)3, or P(OMe)3) with L in the presence of Me3NO to form cis-Mo(CO)4L2. The rates of reactions are second order: first order in Mo(CO)5L concentration, first order in Me3NO concentration, and zero order in L concentration. For ligand L with cone angles less than 135°, the rates of reaction increase with increasing stretching frequency of the CO bands in the IR. This supports the proposed mechanism, which involves attack by the O atom of Me3NO on a C of a CO cis to L in Mo(CO)5L For L = PPh3 or AsPh3, the reactions are faster than expected on the basis of their νCO values, and this is discussed in terms of steric effects.
