New Heterobimetallic .mu.-Oxo Complexes Formed via Halide Displacement Reactions Using the Trioxo Anions [Cp*Mo(O)3]- and [Cp*W(O)3]
Autor: | Gregory L. Geoffroy, Melinda S. Rau, Arnold L. Rheingold, Christine M. Kretz, Brian S. Haggerty |
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Rok vydání: | 1994 |
Předmět: | |
Zdroj: | Organometallics. 13:1624-1634 |
ISSN: | 1520-6041 0276-7333 |
Popis: | 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. |
Databáze: | OpenAIRE |
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