William J. Marshall

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Facile and highly selective perfluoroalkyl-aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50-80 degrees C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by(More)
A series of new complexes [(L-L)Pd(Ar)(CF3)] (L-L = dppe, dppp, tmeda; Ar = Ph, p-Tol, C6D5) have been synthesized and fully characterized in solution and in the solid state. Remarkable Ph-X activation (X = I, Cl) by [(dppe)Pd(Ph)(CF3)] (1) has been found to come about to cleanly produce biphenyl and [(dppe)Pd(Ph)(X)]. This reaction does not take place(More)
The fluoride congener of Wilkinson's catalyst, [(Ph(3)P)(3)RhF] (1), has been synthesized and fully characterized. Unlike Wilkinson's catalyst, 1 easily activates the inert C-Cl bond of ArCl (Ar = Ph, p-tolyl) under mild conditions (3 h at 80 degrees C) to produce trans-[(Ph(3)P)(2)Rh(Ph(2)PF)(Cl)] (2) and ArPh as a result of C-Cl, Rh-F, and P-C bond(More)
[(Ph(3)P)(3)Rh(F)] reacts with CF(3)SiMe(3) to produce trans-[(Ph(3)P)(2)Rh(CF(2))(F)] (1; X-ray), which is equilibrated with a number of species in solution. Addition of excess Ph(3)P shifts all of the equilibria to [(Ph(3)P)(3)Rh(CF(3))] (2; X-ray) as the only NMR-observable and isolable (84%) species. Complex 2 is uniquely highly fluxional in solution,(More)
The fluoro analogue of Wilkinson's catalyst, [(Ph3P)3RhF] (1), was synthesized and fully characterized. Both solution behavior and solid-state geometry parameters of 1 were found to be surprisingly similar to those of Wilkinson's catalyst. Unlike Wilkinson's catalyst however, 1 exhibited most unusual reactivity toward the notoriously inert C-Cl bond of(More)
Increasing evidence supports the notion that both internalizing (e.g., anxiety) and externalizing (e.g., aggression) behavioral dysregulation are associated with abnormal communication between brain regions. Electroencephalographic (EEG) signals across two electrode sites are said to be coherent with one another when they show consistent phase relations.(More)
An application of the new sterically hindered electron-poor 2-(3,5-bis(trifluoromethyl)phenyl)-4-trifluoromethylpyridine [HC--N] (1) in the one-step high temperature cyclometalation by Ir(III)Cl3 in the presence of Ag(I)OC(O)CF3 resulted in the synthesis of tris-cyclometalated complexes [C--N]2Ir[C--C] (3) and [C--N]3Ir (5). A neutral silver cluster with a(More)
A bimetallic carbene complex architecture that incorporates a cyclopentadienyl-annulated imidazol-2-ylidene moiety is characterized. The ligand architecture enables direct electronic interaction between the pi- and sigma-bonded metals. A preliminary example of aqueous Suzuki coupling employing a metallocene-fused imidazol-2-ylidene-derived catalyst is(More)