Cyclopentoxyditungsten compounds and crystal and molecular structures and dynamic solution behavior of W sub 2 (. mu. -H)(O-c-C sub 5 H sub 9 ) sub 7 (HNMe sub 2 )
- Indiana Univ., Bloomington (United States)
The reaction between W{sub 2}(NMe{sub 2}){sub 6} and cyclopentanol ({ge}6 equiv) in hexane solvents initially forms the dimethylamine adduct W{sub 2}(O-c-C{sub 5}H{sub 9}){sub 6}(HNMe{sub 2}){sub 2} but with time in the presence of cyclopentanol and dimethylamine the hydrido-bridged compound W{sub 2}({mu}-H)(O-c-C{sub 5}H{sub 9}){sub 7}(HNMe{sub 2}) is formed and may be isolated as green crystals. Crystal data at {minus}155C: a = 13.057 (3) {angstrom}, b = 15.592 (4) {angstrom}, c = 10.376 (2) {angstrom}, {alpha} = 97.72 (1){degree},{beta} = 109.55 (1){degree}, {gamma} = 94.22 (1){degree}, {zeta} = 2,d{sub calcd} = 1.738 g cm{sup {minus}3}, and space group P1. The bridging hydride was not located crystallographically but can be inferred to occupy a position trans to the HNME{sub 2} ligand so as to complete a confacial bioctahedron. In solution, the molecule is fluxional and the dimethylamine is labile and has been replace by PMe{sub 3}. Variable-temperature H and P NMR studies reveal that the (RO){sub 3}W({mu}-H)({mu}-OR){sub 2}W(OR){sub 2}(L) molecules are in a temperature dependent equilibrium with the unligated molecule W{sub 2}({mu}-h)(or){sub 7} and the free ligand. At high temperature, rapid OR group scrambling generates two equivalent (time-averaged) W atoms, but at low temperature the NMR spectra are consistent with expectations based on the solid-state structure of W{sub 2}({mu}-H)(O-c-C{sub 5}H{sub 9}){sub 7}(HNMe{sub 2}).
- OSTI ID:
- 5975103
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 30:16; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKOXIDES
CRYSTAL STRUCTURE
MOLECULAR STRUCTURE
CYCLOALKENES
ORGANIC NITROGEN COMPOUNDS
TUNGSTEN COMPOUNDS
EXPERIMENTAL DATA
NMR SPECTRA
PHOSPHORUS 31
PROTONS
ALKENES
BARYONS
DATA
ELEMENTARY PARTICLES
FERMIONS
HADRONS
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS ISOTOPES
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation