Facile interconversions of alkyne and vinylidene ligands on divalent molybdenum and tungsten
Molybdenum alkynyls trans-(M(C/identical to/CCMe/sub 3/)L-(PR/sub 3/)/sub 2/(Cp)) are prepared by deprotonation of (Mo(HC/identical to/CCMe/sub 3/)(PR/sub 3/)/sub 2/(Cp))/sup +/ PR/sub 3/ = P(OMe)/sub 3/; PR/sub 3/ = PMe/sub 2/Ph using NaN(SiMe/sub 3/)/sub 2/ in the presence of CO or P(OMe)/sub 3/. Protonation of (Mo(C/identical to/CMe/sub 3/)(CO)(P(OMe)/sub 3/)/sub 2/(Cp)) at /minus/78/degree/C gives trans-(Mo(C/emdash/CHCMe/sub 3/)(CO)(P(OMe)/sub 3/)/sub 2/(Cp))(X), which decarbonylates above 0/degree/C (X = BF/sub 4/) or is trapped by excess triflic acid (HOTf) to give the alkylidyne complex trans-(Mo(/identical to/CCH/sub 2/CMe/sub 3/)(OTf)(P(OMe)/sub 3/)/sub 2/(Cp)) (Otf). Protonation of (Mo(C/identical to/CCMe/sub 3/)(CO)(PMe/sub 2/Ph)/sub 2/(Cp)) with HOTf gives stable trans-(Mo(C/emdash/CHCMe/sub 3/(CO))(PMe/sub 2/Ph)/sub 2/(Cp))(OTf), while exposure of (Mo(HC/identical to/CCMe/sub 3/)(PMe/sub 2/Ph)/sub 2/(Cp))(BF/sub 4/) to 1 atm of CO effects is conversion to trans-(Mo(C/emdash/CHCMe/sub 3/)(CO)(PMe/sub 2/PH)/sub 2/(Cp))(BF/sub 4/). The structure of trans-(W(C/emdash/CMePh)(CO)(P(OMe)/sub 3/)/sub 2/(Cp))(PF/sub 6/) was determined by X-ray diffraction (R = 3.3%, R/sub w/ = 4.0%).
- Research Organization:
- Univ. of Kentucky, Lexington (USA)
- OSTI ID:
- 6048283
- Journal Information:
- Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:10; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
BARYONS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HADRONS
INFORMATION
LIGANDS
MOLYBDENUM COMPLEXES
NUCLEONS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PROTONS
SCATTERING
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
VALENCE
X-RAY DIFFRACTION
YIELDS