Michael R. Duttera, V. Day, T. Marks
1984
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Journal
Journal of the American Chemical Society
Abstract
A study of the reaction of the organoactinide hydrides (Cp'/sub 2/MH/sub 2/)/sub 2/ (Cp' = eta/sup 5/-(CH/sub 3/)/sub 5/C/sub 5/, M = Th, U) with trimethyl phosphite is reported. Quantitative transposition of hydride and methoxide ligands occurs to yield the corresponding Cp'/sub 2/M(OCH/sub 3/)/sub 2/ complexes (synthesized independently from Cp'/sub 2/MCl/sub 2/ and NaOCH/sub 3/) and the phosphinidene-bridged methoxy complexes (Cp'/sub 2/M(OCH/sub 3/))/sub 2/PH. The reaction is considerably more rapid for M = U than for M = Th. The new compounds were characterized by elemental analysis, /sup 1/H and /sup 31/P NMR, infrared spectroscopy, magnetic susceptibility, and D/sub 2/O hydrolysis. The molecular structure of (Cp'/sub 2/U(OCH/sub 3/))/sub 2/PH has been determined by single-crystal X-ray diffraction techniques. It crystallizes in the monoclinic space group P2/n with a = 13.926 (3) A, b = 10.765 (3) c = 15.282 (4) A, ..beta.. = 107.63 (2)/sup 0/, and Z = 2. Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R/sub 1/ (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2 theta/sub MoK..cap alpha../ 3sigma(I). The (Cp'/sub 2/U(OCH/sub 3/))/sub 2/PH molecule has C/sub 2/more » symmetry, with the ..mu..-PH/sup 2 -/ ligand lying on a crystallographic twofold axis. The coordination geometry about each uranium ion is of the typical pseudotetrahedral Cp'/sub 2/M(X)T type, with U-P = 2.743 (1) A, U-O = 2.046 (14) A, angle U-P-U = 157.7 (2)/sup 0/, and angle U-O-C (methyl) = 178 (1)/sup 0/. Evidence is presented that other > P-OR linkages react in a similar manner.« less