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

Michael R. Duttera, Victor W. Day, Tobin J Marks

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Abstract

This contribution reports a study of the reaction of the organoactinide hydrides (Cp′2MH2)2 (Cp′ = η5-(CH3)5C5, M = Th, U) with trimethyl phosphite. Quantitative transposition of hydride and methoxide ligands occurs to yield the corresponding Cp′2M(OCH3)2 complexes (synthesized independently from Cp′2MCl2 and NaOCH3) and the phosphinidene-bridged methoxy complexes [Cp′2M(OCH3)]2PH. The reaction is considerably more rapid for M = U than for M = Th. The new compounds were characterized by elemental analysis, 1H and 31P NMR, infrared spectroscopy, magnetic susceptibility, and D2O hydrolysis. The molecular structure of [Cp′2U(OCH3)]2PH has been determined by single-crystal X-ray diffraction techniques. It crystallizes in the monoclinic space group P2/n with a = 13.926 (3) Å, b = 10.765 (3) Å, c = 15.282 (4) Å, β = 107.63 (2)°, and Z = 2. Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R1 (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2θMoKα <43° and I > 3σ(I). The [Cp′2U(OCH3)]2PH molecule has C2 symmetry, with the μ-PH2- ligand lying on a crystallographic twofold axis. The coordination geometry about each uranium ion is of the typical "pseudotetrahedral" Cp′2M(X)Y type, with U-P = 2.743 (1) Å, U-O = 2.046 (14) Å, 〈U-P-U = 157.7 (2)°, and 〈U-O-C(methyl) = 178 (1)°. Evidence is presented that other >P-OR linkages react in a similar manner.

Original languageEnglish
Pages (from-to)2907-2912
Number of pages6
JournalJournal of the American Chemical Society
Volume106
Issue number10
Publication statusPublished - 1984

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phosphine
Actinoid Series Elements
Phosphites
trimethyl phosphite
Actinides
Hydrides
Ligands
Uranium
Molecular Structure
Least-Squares Analysis
Magnetic susceptibility
X-Ray Diffraction
Molecular structure
Infrared spectroscopy
Hydrolysis
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Single crystals
Ions
X ray diffraction

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{315833bccc78461d9e3edc02c0913f2a,
title = "Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes",
abstract = "This contribution reports a study of the reaction of the organoactinide hydrides (Cp′2MH2)2 (Cp′ = η5-(CH3)5C5, M = Th, U) with trimethyl phosphite. Quantitative transposition of hydride and methoxide ligands occurs to yield the corresponding Cp′2M(OCH3)2 complexes (synthesized independently from Cp′2MCl2 and NaOCH3) and the phosphinidene-bridged methoxy complexes [Cp′2M(OCH3)]2PH. The reaction is considerably more rapid for M = U than for M = Th. The new compounds were characterized by elemental analysis, 1H and 31P NMR, infrared spectroscopy, magnetic susceptibility, and D2O hydrolysis. The molecular structure of [Cp′2U(OCH3)]2PH has been determined by single-crystal X-ray diffraction techniques. It crystallizes in the monoclinic space group P2/n with a = 13.926 (3) {\AA}, b = 10.765 (3) {\AA}, c = 15.282 (4) {\AA}, β = 107.63 (2)°, and Z = 2. Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R1 (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2θMoKα <43° and I > 3σ(I). The [Cp′2U(OCH3)]2PH molecule has C2 symmetry, with the μ-PH2- ligand lying on a crystallographic twofold axis. The coordination geometry about each uranium ion is of the typical {"}pseudotetrahedral{"} Cp′2M(X)Y type, with U-P = 2.743 (1) {\AA}, U-O = 2.046 (14) {\AA}, 〈U-P-U = 157.7 (2)°, and 〈U-O-C(methyl) = 178 (1)°. Evidence is presented that other >P-OR linkages react in a similar manner.",
author = "Duttera, {Michael R.} and Day, {Victor W.} and Marks, {Tobin J}",
year = "1984",
language = "English",
volume = "106",
pages = "2907--2912",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "10",

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T1 - Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes

AU - Duttera, Michael R.

AU - Day, Victor W.

AU - Marks, Tobin J

PY - 1984

Y1 - 1984

N2 - This contribution reports a study of the reaction of the organoactinide hydrides (Cp′2MH2)2 (Cp′ = η5-(CH3)5C5, M = Th, U) with trimethyl phosphite. Quantitative transposition of hydride and methoxide ligands occurs to yield the corresponding Cp′2M(OCH3)2 complexes (synthesized independently from Cp′2MCl2 and NaOCH3) and the phosphinidene-bridged methoxy complexes [Cp′2M(OCH3)]2PH. The reaction is considerably more rapid for M = U than for M = Th. The new compounds were characterized by elemental analysis, 1H and 31P NMR, infrared spectroscopy, magnetic susceptibility, and D2O hydrolysis. The molecular structure of [Cp′2U(OCH3)]2PH has been determined by single-crystal X-ray diffraction techniques. It crystallizes in the monoclinic space group P2/n with a = 13.926 (3) Å, b = 10.765 (3) Å, c = 15.282 (4) Å, β = 107.63 (2)°, and Z = 2. Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R1 (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2θMoKα <43° and I > 3σ(I). The [Cp′2U(OCH3)]2PH molecule has C2 symmetry, with the μ-PH2- ligand lying on a crystallographic twofold axis. The coordination geometry about each uranium ion is of the typical "pseudotetrahedral" Cp′2M(X)Y type, with U-P = 2.743 (1) Å, U-O = 2.046 (14) Å, 〈U-P-U = 157.7 (2)°, and 〈U-O-C(methyl) = 178 (1)°. Evidence is presented that other >P-OR linkages react in a similar manner.

AB - This contribution reports a study of the reaction of the organoactinide hydrides (Cp′2MH2)2 (Cp′ = η5-(CH3)5C5, M = Th, U) with trimethyl phosphite. Quantitative transposition of hydride and methoxide ligands occurs to yield the corresponding Cp′2M(OCH3)2 complexes (synthesized independently from Cp′2MCl2 and NaOCH3) and the phosphinidene-bridged methoxy complexes [Cp′2M(OCH3)]2PH. The reaction is considerably more rapid for M = U than for M = Th. The new compounds were characterized by elemental analysis, 1H and 31P NMR, infrared spectroscopy, magnetic susceptibility, and D2O hydrolysis. The molecular structure of [Cp′2U(OCH3)]2PH has been determined by single-crystal X-ray diffraction techniques. It crystallizes in the monoclinic space group P2/n with a = 13.926 (3) Å, b = 10.765 (3) Å, c = 15.282 (4) Å, β = 107.63 (2)°, and Z = 2. Full-matrix least-squares refinement of the structural parameters for the 24 independent anisotropic non-hydrogen atoms has converged to R1 (unweighted, based on F) = 0.041 for 1677 independent absorption-corrected reflections having 2θMoKα <43° and I > 3σ(I). The [Cp′2U(OCH3)]2PH molecule has C2 symmetry, with the μ-PH2- ligand lying on a crystallographic twofold axis. The coordination geometry about each uranium ion is of the typical "pseudotetrahedral" Cp′2M(X)Y type, with U-P = 2.743 (1) Å, U-O = 2.046 (14) Å, 〈U-P-U = 157.7 (2)°, and 〈U-O-C(methyl) = 178 (1)°. Evidence is presented that other >P-OR linkages react in a similar manner.

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