Oxygen atom transfer from a phosphine oxide to tungsten(II) compounds
- Univ. of Washington, Seattle (United States)
WCl{sub 2}(PMePh{sub 2}){sub 4} (1) reacts rapidly with Ph{sub 2}P(O)CH{sub 2}CH{sub 2}PPh{sub 2} (5, the monooxide of diphos) to give an adduct, WCl{sub 2}(Ph{sub 2}P(O)Ch{sub 2}CH{sub 2}PPh{sub 2})(PMePh{sub 2}){sub 2} (6). On being heated at 80C for 8 h, 6 rearranges by transferring the phosphoryl oxygen to tungsten, with the formation of tungsten-oxo complexes W(O)Cl{sub 2}(diphos)(PMePh{sub 2}) (7) and W(O)Cl{sub 2}(PMEPh{sub 2}){sub 3} (2), as well as WCl{sub 2}(diphos)(PMePh{sub 2}){sub 2} (8). This is the first example of oxygen atom transfer from a phosphine oxide to a metal center, a remarkable reaction because of the strength of the P-O bond (roughly 130 kcal/mol). The presence of an oxygen atom transfer step in this reaction has been confirmed by oxygen-18-labeling studies. WCl{sub 2}(PMe{sub 3}){sub 4} (9) also deoxygenates 5, forming similar and 9 indicating that the chelating nature of 5 is needed to assist the initial coordination of the phosphoryl oxygen. The kinetic barriers to deoxygenation of phosphine oxides lie both in the initial coordination of the phosphine oxide and in the actual oxygen atom transfer step. Allyl- and vinylphosphine oxides also react with 1, but oxygen atom transfer from these substrates has not been observed. 34 refs., 2 figs., 3 tabs.
- OSTI ID:
- 6106576
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:9; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ALKENES
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EVEN-EVEN NUCLEI
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
ISOTOPES
LABELLED COMPOUNDS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXIDATION
OXYGEN 18
OXYGEN ISOTOPES
STABLE ISOTOPES
SYNTHESIS
TEMPERATURE EFFECTS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES