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Density functional theory (DFT, B3PW91) calculations have been carried out on the reactivity of ethene with model systems M(NR)(=CHCH3)(X)(Y) for M = Mo or W, R = methyl or phenyl, X = CH2CH3, OCH3, or OSiH3, and Y = CH2CH3, OCH3, or OSiH3, which are representative of experimental olefin metathesis catalysts, and the results are compared to those previously(More)
DFT(B3PW91) calculations have been carried out to rationalise the structural, electronic and spectroscopic properties of Mo and W imido M(NR1)(CHR2)(X)(Y) olefin metathesis catalysts by using either simplified or actual ligands of the experimental complexes. The calculated structures, energetics (preference for the syn isomer and alkylidene rotational(More)
DFT(B3PW91) calculations show that release of H2 is greatly favored thermodynamically in five membered rings over six and by the incorporation of N atoms into the rings, either as ring atoms or as ring substituents, particularly in 1,3 positions.
N,N'-Disubstituted imidazolium carboxylates, readily synthetically available, isolable, air- and water-stable reagents, efficiently transfer N-heterocyclic carbene (NHC) groups to Rh, Ir, Ru, Pt, and Pd, to give novel NHC complexes, e.g., [Pd(NHC)3OAc]OAc and [Pt(NHC)3Cl]Cl (NHC = 1,3-dimethyl imidazol-2-ylidene). The NHC esters are also effective. Tuning(More)
C-H bond activation of fluorinated aromatic hydrocarbons by [Tp'Rh(CNneopentyl)] resulted in the formation of products of the type Tp'Rh(CNneopentyl)(aryl(F))H. The stability of the Rh-C(aryl) product is shown to be strongly dependent on the number of ortho fluorines and only mildly dependent on the total number of fluorine substituents. Complexes with aryl(More)
We report a series of hydroarylations of unactivated olefins with trifluoromethyl-substituted arenes that occur with high selectivity for the linear product without directing groups on the arene. We also show that hydroarylations occur with internal, acyclic olefins to yield linear alkylarene products. Experimental mechanistic data provide evidence for(More)
DFT methods are used to quantify the relationship between M-C and H-C bond energies; for MLn = Re(eta5-C5H5)(CO)2H and fluorinated aryl ligands, theoretical and experimental investigations of ortho-fluorine substitution indicate a much larger increase in the M-C than in the H-C bond energy, so stabilising C-H activation products.
Protonation of the ortho-metalated ruthenium complexes RuH(H(2))(X)(P(i)Pr(3))(2) [X = 2-phenylpyridine (ph-py) (1), benzoquinoline (bq) (2)] and RuH(CO)(ph-py)(P(i)Pr(3))(2) (3) with [H(OEt(2))(2)](+)[BAr'(4)](-) (BAr'(4) = [(3,5-(CF(3))(2)C(6)H(3))(4)B]) under H(2) atmosphere yields the corresponding cationic hydrido dihydrogen ruthenium complexes(More)
A question of coordination mode: Two new borane compounds are prepared. They act as bifunctional ligands as illustrated by their reaction with ruthenium polyhydrides which leads to the formation of two complexes (see scheme) displaying either a delta-agostic interaction of a eta(2)-B-H bond involving a trivalent boron atom or a dihydroborate ligation.
A series of complexes of the type Tp'Rh(PR(3))(Ar(F))H, where PR(3) = PMe(3) (3) and PMe(2)Ph (9), Ar(F) = C(6)F(5) (a), 2,3,4,5-C(6)F(4)H (b), 2,3,5,6-C(6)F(4)H (c), 2,4,6-C(6)F(3)H(2) (d), 2,3-C(6)F(2)H(3) (e), 2,5-C(6)F(2)H(3) (g), and 2-C(6)FH(4) (h) and Tp' = tris(3,5-dimethylpyrazolyl)borate, has been synthesized as stable crystalline compounds by the(More)