192221-01-5Relevant academic research and scientific papers
Monohydride complexes of W(IV) containing bulky selenolate ligands: X-ray crystal structure determination of [WH(SeC6H3Pri 2-2,6)3(PMe2Ph)2]
Burrow,Lough,Richards,Morris
, p. 125 - 135 (2008/10/08)
The complexes [WH(SeR)3(L)(PMe2Ph)] (R = C6H3Pri 2-2,6 or C6H2Me3-2,4,6; L = PMe2Ph, pyridine and N-methylimidazole) have been prepared by reaction of [WH6(PMe2Ph)3] or cis-[W(N2)2(PMe2Ph)4] with the selenol HSeR and characterized by FAB mass spectroscopy, 31P, 1H and 77Se NMR, IR and UV-Vis spectroscopies. A single crystal X-ray diffraction study of complex [WH(SeC6H3Pri 2-2,6)3(PMe2Ph)2] at 178 K reveals a distorted trigonal bipyramidal geometry of the WSe3P2 core with the hydride located along an Se-P edge of the trigonal bipyramid; the hydride position was refined with a W-H distance of 1.51(6) A and an H-W-P angle of 53°. This small angle results in a large 2J(H,P) coupling of 99 Hz. The bulky Se ligands adopt a 'two-up, one-down' arrangement of aryl substituents. The 2J(SeP) values show a high degree of dependence on the P-M-Se angles or the P-M-Se-C dihedral angle. This may be useful for assigning geometries of selenolate complexes. Improved syntheses of the starting compounds [WH6(PMe2Ph)3] and cis-[W(N2)2(PMe2Ph)4] are reported.
