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New heterobimetallic [mu]-oxo complexes formed via halide displacement reactions using the trioxo anions [Cp*Mo(O)[sub 3]][sup [minus]] and [Cp*W(O)[sub 3]][sup [minus]]

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00017a020· OSTI ID:7166004
; ;  [1]; ;  [2]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Univ. of Delaware, Newark, DE (United States)
+ Show Author Affiliations
The trioxo anions [Cp*W(O)[sub 3]][sup [minus]] and [Cp*Mo(O)[sub 3]][sup [minus]] have been shown to be useful reagents for the formation of [mu]-oxo complexes via halide displacement reactions. For example, they react with Cp*M(O)[sub 2]Cl (M = Mo, W) to form the known homometallic [mu]-oxo complexes Cp*(O)[sub 2]M-O-M(O)[sub 2]Cp* along with the heterometallic complex Cp*(O)[sub 2]Mo-O-W(O)[sub 2]Cp*. This latter species was also observed to form via a metal exchange process upon mixing the homometallic complexes Cp*(O)[sub 2]Mo-O-Mo(O)[sub 2]Cp* and Cp*(O)[sub 2]W-O-W(O)[sub 2]Cp*. Reaction of the trioxo anions with Cp[sub 2]M[prime]Cl[sub 2] led to the new heterobimetallic complexes Cp[sub 2]M[prime](Cl)-O-M(O)[sub 2]Cp* (M[prime] = Ti, Zr, M = Mo, W; M[prime] = V, M = W). The corresponding trinuclear complexes Cp*(O)[sub 2]W-O-M[prime](Cp)[sub 2]-O-W(O)[sub 2]Cp* were formed via addition of 2 equiv of [Cp*W(O)[sub 3]][sup [minus]] to Cp[sub 2]M[prime]Cl[sub 2] (M[prime] = Ti,Zr). Addition of Et[sub 2]O to Cp[sub 2] V(Cl)-O-W(O)[sub 2]Cp* gave the solvated complex [Cp[sub 2]V(Et[sub 2]O)-O-W(O)[sub 2]Cp*]Cl, and the tetrametallic complex [(Cp[sub 2]Ti)[sub 2](Cp*W(O)[sub 2])[sub 2]([mu]-O)[sub 4]][BPh[sub 4]][sub 2] was produced via halide abstraction from Cp[sub 2]Ti(Cl)-O-W(O)[sub 2]Cp* with Na[BPh[sub 4]] followed by dimerization of the resulting monocations. 15 refs., 6 figs., 5 tabs.
OSTI ID:
7166004
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:5; ISSN 0276-7333; ISSN ORGND7
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
CATALYSTS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DIFFRACTION
GERMANIUM COMPOUNDS
HALOGEN COMPOUNDS
LIGANDS
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
RESONANCE
SCATTERING
SILICON COMPOUNDS
TIN COMPOUNDS
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
VANADIUM COMPLEXES
X-RAY DIFFRACTION
ZIRCONIUM COMPLEXES