Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes

Journal Article · Wed May 16 04:00:00 EDT 1984 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00322a028· OSTI ID:6680749

Duttera, M R; Day, V W; Marks, T J

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../ < 43/sup 0/ and I > 3sigma(I). The (Cp'/sub 2/U(OCH/sub 3/))/sub 2/PH molecule has C/sub 2/ 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.

• Research Organization: Northwestern Univ., Evanston, IL
• OSTI ID: 6680749
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 106:10; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry &amp; Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DECOMPOSITION
DIFFRACTION
EXPERIMENTAL DATA
HEAVY WATER
HYDROGEN COMPOUNDS
HYDROLYSIS
INFORMATION
INFRARED SPECTRA
INORGANIC ACIDS
LYSIS
MAGNETIC PROPERTIES
MAGNETIC SUSCEPTIBILITY
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHOROUS ACID
PHOSPHORUS COMPOUNDS
PHYSICAL PROPERTIES
SCATTERING
SOLVOLYSIS
SPECTRA
SYNTHESIS
THORIUM COMPLEXES
URANIUM COMPLEXES
WATER
X-RAY DIFFRACTION