Stella A Gonsales

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Tungsten alkylidynes [CF3-ONO]W≡CC(CH3)3(THF)2 (1) and [(t)BuOCO]W≡CC(CH3)3(THF)2 (3) react with ethylene. Complex 1 reacts reversibly with ethylene to give the metallacyclobutene (2). Complex 3 reacts with ethylene to form the tethered alkylidene (4) featuring a tetraanionic pincer ligand. Complexes 1 and 3 initiate the polymerization of norbornene at room(More)
The tungsten alkylidyne [(t)BuOCO]W≡C((t)Bu) (THF)2 (1) reacts with CO2, leading to complete cleavage of one C═O bond, followed by migratory insertion to generate the tungsten-oxo alkylidene 2. Complex 2 is the first catalyst to polymerize norbornene via ring expansion metathesis polymerization to yield highly cis-syndiotactic cyclic polynorbornene.
The tungsten alkylidyne [CF3-ONO]W≡CC(CH3)3(THF)2 (3) {where CF3-ONO = (MeC6H3[C(CF3)2O])2N(3-)} supported by a trianionic pincer-type ligand demonstrates enhanced nucleophilicity in unusually fast "Wittig-like" reactions. Experiments are designed to provide support for an inorganic enamine effect that is the origin of the enhanced nucleophilicity. Treating(More)
The cleavage of carbon dioxide by the tungsten alkylidyne [CF3-ONO]W[triple bond, length as m-dash]CC(t)Bu(THF)2 (1) {where CF3-ONO = (MeC6H3[C-(CF3)2O])2N(3-)}, is reported. Splitting of CO2 yields the tungsten oxo ketene complex [CF3-ONO]W(O){(CH3)3CC[double bond, length as m-dash]C[double bond, length as m-dash]O} (6). The proposed pathway occurs through(More)
The trianionic pincer supported tungsten-vinyl complex [CF3-ONO]W(O){(CH3)3CC[double bond, length as m-dash]C(CH3)2} (3syn) undergoes facile double bond rotation at ambient temperature. The degenerate methyl exchange rates were measured via selective inversion-recovery experiments. DFT computations in conjunction with experimentally determined rate(More)
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