Synthesis, isolation, and spectroscopic characterization of trivanadium polyoxoanion-supported (C{sub 5}H{sub 5})Ti{sup 3+}: (Bu{sub 4}N){sub 4}[CpTi-SiW{sub 9}V{sub 3}O{sub 40}] and (Bu{sub 4}N){sub 6}[CpTi{lg_bullet}P{sub 2}W{sub 15}V{sub 3}O{sub 62}]
- Pacific Northwest Laboratories, Richland, WA (United States)
- Univ. of Oregon, Eugene, OR (United States)
- Colorado State Univ., Ft. Collins, CO (United States)
Reaction of the trivanadium-substituted polyoxometalates (Bu{sub 4}N){sub 7}SiW{sub 9}V{sub 3}O{sub 40} and (Bu{sub 4}N){sub 9}P{sub 2}W{sub 15}V{sub 3}O{sub 62} with an equimolar amount of CpTi{sup 3+} leads to the formation of the polyoxometalate-supported organometallic complexes [CpTi{lg_bullet}SiW{sub 9}V{sub 3}O{sub 40}]{sup 4{minus}}, 1, and [CpTi{lg_bullet}P{sub 2}W{sub 15}V{sub 3}O{sub 62}]{sup 6{minus}}, 2, respectively. These complexes were isolated as their Bu{sub 4}N{sup +} salts and subsequently characterized by a complete elemental analysis and {sup 31}P, {sup 183}W, {sup 51}V, and {sup 1}H NMR spectroscopy as well as FAB-MS,IR, and sedimentation-equilibrium molecular-weight measurements. For compound 1 additional data in the form of 2-D INADEQUATE {sup 183}W{sup 51V} NMR spectra were collected. Both 1 and 2 are homogeneous, regiospecifically supported CpTi{sup 3+} complexes of overall C{sub s} symmetry. Solution structures, derived from and in accord with the observed spectroscopic data, are proposed. The synthesis and initial solution spectroscopic characterization of the non-cyclopentadienyl, ClTi{sup 3+} complex, ClTi{lg_bullet}SiW{sub 9}V{sub 3}O{sub 40}{sup 4{minus}}, is also reported, a nominally highly coordinatively unsaturated Ti(IV) complex on route to more reactive catalyst precursors.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 422079
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 17 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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