110433-32-4Relevant academic research and scientific papers
Synthesis, reactivity, and X-ray structure of fac-W(CO)3(dppm) (CH3CN). Stereoselective preparation of fac-W(CO)3(13CO) (dppm) and subsequent intramolecular rearrangement processes
Darensbourg, Donald J.,Zalewski, David J.,Plepys, Christine,Campana, Charles
, p. 3727 - 3732 (2008/10/08)
The reaction of fac-W(CO)3(CH3CN)3 with an equimolar quantity of bis(diphenylphosphino)methane (dppm) results in the quantitative formation of fac-W(CO)3(dppm)(CH3CN). The solid-state structure of fac-W(CO)3(dppm)(CH3CN) was established by X-ray diffraction [P21/c (monoclinic), a = 10.937 (2) ?, b = 18.399 (4) ?, c = 15.194 (3) ?, β = 108.33 (1)°, Z = 4]. This compound reacts with 13CO to afford stereoselective fac-W(CO)3(13CO)(dppm). The reaction proceeds by a dissociative pathway, with activation parameters for loss of CH3CN being ΔH? = 23.5 kcal/mol and ΔS? = -6.0 eu. In a subsequent, intramolecular ligand rearrangement facial ? meridional isomerization occurs. Reaction of fac-W(CO)3(dppm)(CH3CN) with an additional 1 mol of dppm leads initially to formation of fac-W(CO)3(dppm)2, which contains both bidentate and monodentate dppm ligands. Isomerization and oxidation of the unattached phosphine eventually provided mer-W(CO)3(dppm)(Ph2PCH2P(O)Ph2). The structure of the latter species was determined by X-ray diffraction [P41 (tetragonal), a = 11.186 (4) ?, c = 40.498 (9) ?, Z = 4].
