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Molecular hydrogen complexes of the transition metals. 3. Preparation, structure, and reactivity of W(CO)/sub 3/(PCy/sub 3/)/sub 2/ and W(CO)/sub 3/(P(i-Pr)/sub 3/)/sub 2/, eta/sup 2/-H/sub 2/ complex precursors exhibiting M. H-C interaction

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00269a027· OSTI ID:5455678
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The synthesis, reactivity, and molecular structures of coordinatively and electronically unsaturated complexes M(CO)/sub 3/(PR/sub 3/)/sub 2/ (M = Mo, W; R = Cy, i-Pr) are described. Ligands that bind reversibly to W(CO)/sub 3/(PCy/sub 3/)/sub 2/ include H/sub 2/, N/sub 2/, C/sub 2/H/sub 4/, H/sub 2/O, ROH, and thiophene; irreversibly bound ligands are MeCN, pyridine, NH/sub 3/, CyNH/sub 2/, and PR/sub 3/. The structures of W(CO)/sub 3/(PCy/sub 3/)/sub 2/ and W(CO)/sub 3/(P(i-Pr)/sub 3/)/sub 2/ involve incipient intramolecular oxidative addition of a distal phosphine C-H bond to the metal. The three-center M...H-C interaction in W(CO)/sub 3/(PCy/sub 3/)/sub 2/ has W-H(11a)-C(11) = 127.6/sup 0/, W-C(11) = 2.945 (6) A, and W-H(11a) approx. 2.27 A. Crystal data for W(CO)/sub 3/(PCy/sub 3/)/sub 2/ are the following: space group P1, a = 10.300 (1) A, b = 12.675 (2) A, c = 15.473 (1) A, ..cap alpha.. = 91.44 (1)/sup 0/, ..beta.. = 90.37 (1)/sup 0/, ..gamma.. = 103.99 (1)/sup 0/, Z = 2, rho(calcd) = 1.34 g cm/sup -3/, R = 0.025, 6211 reflections. Crystal data for W(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/ are the following: P2/sub 1//m, a = 8.425 (1) A, b = 13.375 (2) A, c = 12.039 (2) A, ..beta.. = 109.58 (1)/sup 0/, Z = 2, rho(calcd) = 1.53 g cm/sup -3/, R = 0.034, 2212 reflections. Since these molecules add dihydrogen to form stable eta/sup 2/-H/sub 2/ complexes, they afford an unprecedented opportunity to observe both H-H and C-H bond activation at a single metal center.
Research Organization:
Los Alamos National Lab., NM
OSTI ID:
5455678
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:9; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BOND ANGLE
BOND LENGTHS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
EXPERIMENTAL DATA
HYDROGEN COMPLEXES
INFORMATION
LATTICE PARAMETERS
LENGTH
LIGANDS
MOLECULES
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
SCATTERING
SPACE GROUPS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION