Synthesis, characterization, low-temperature (50 K) neutron diffraction structure, and reactivity of chlorodihydridotetrakis(trimethylphosphine)tantalum (III)
Dichlorodihydridotetrakis(trimethylphosphine)tantalum(IV), TaCl/sub 2/H/sub 2/(PMe/sub 3/)/sub 4/, is reduced under argon by sodium amalgam in the presence of PMe/sub 3/ to give green TaClH/sub 2/(PMe/sub 3/)/sub 4/ (1a) in 70% yield. 1a has been characterized by spectroscopy, variable-temperature /sup 1/H and /sup 31/P(/sup 1/H) NMR spectroscopy, and low-temperature (50K) neutron crystallography. In the solid state, 1a is a slightly distorted pentagonal bipyramid with two axial phosphines. The hydride ligands are coordinated in a cis configuration in the pentagonal plane with a H-Ta-H angle of 66.2 (6)/sup 0/ and Ta-H distances of 1.79 (1) and 1.80 (1) A. 1a reacts readily with Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/ (dmpe) to give TaClH/sub 2/(dmpe)/sub 2/ (2) and with ethylene to give TaCL(C/sub 2/H/sub 4/)(PMe/sub 3/)/sub 4/ (3). It also reacts with dinitrogen to given the ..mu..-dinitrogen complex (TaClH/sub 2/(PMe/sub 3/)/sub 3/)/sub 2/(..mu..-N/sub 2/) (4a) and with carbon monoxide to provide TaCl(CO)/sub 3/(PMe/sub 3/)/sub 3/ (5). The latter complex has been characterized by low-temperature (-160/sup 0/C) X-ray crystallography. In the solid state, 5 is a capped (by Cl) trigonal prism with three PMe/sub 3/ ligands and one CO on the capped quadrilateral face and two CO ligands on the remaining edge. Crystal data for 1a (at 50 K) and for 5 are presented. 25 references, 5 figures, 6 tables.
- Research Organization:
- Univ. of Michigan, Ann Arbor
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 5572148
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:15; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
BARYONS
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HADRONS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NEUTRON DIFFRACTION
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
PHOSPHINES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
PROTONS
REFRACTORY METAL COMPOUNDS
RESONANCE
SCATTERING
STABLE ISOTOPES
SYNTHESIS
TANTALUM CHLORIDES
TANTALUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS