The mechanisms for the interconversion of facial diastereomers of a variety of TpRe(CO)(L)(eta(2)-L(Ar)) complexes [L = (t)BuNC, pyridine (py), PMe(3), or 1-methylimidazole (MeIm); L(Ar) = benzene, anisole, naphthalene, 1-methylpyrrole, furan, or thiophene; Tp = hydridotris(pyrazolyl)borate] have been investigated by (1)H NMR spin saturation experiments. In addition, the rates and free energies of activation for these processes were calculated from spin saturation experiments and T(1) measurements. The operative mechanisms for interconversion of the pi diastereomers were found to be nondissociative, undergoing either an interfacial or intrafacial linkage isomerization. A comparison of the kinetic parameters for isomerization of related eta(2)-olefin complexes of the [TpRe(CO)(PMe(3))] and [CpRe(NO)(PPh(3))](+) fragments is also presented.

The π-basic metal fragment {TpRe(CO)-(MeIm)} (MeIm ) 1-methylimidazole; Tp ) hydridotris-(pyrazolyl)borate) binds a variety of aromatic molecules, including benzene, 2,6-lutidine, and 1-methylpyrrole, in an η 2 fashion. Although TpRe(CO)(MeIm)(η 2 -benzene) as a solid shows no decomposition over several months at 25 °C under a nitrogen atmosphere, the complex has proven to be a valuable precursor to a variety of other aromatic complexes through ligand exchange reactions in solution.

A mixture of the tungsten allylimido complexes Cl(4)(RCN)W(NC(3)H(5)) (3a, R = CH(3) and 3b, R = Ph) was tested as a single-source precursor for growth of tungsten nitride (WN(x)) or carbonitride (WN(x)C(y)) thin films. Films deposited from 3a,b below 550 degrees C contained amorphous beta-WN(x)C(y), while those deposited at higher temperatures were polycrystalline. Film growth rates from 3a,b ranged from 5 to 10 A/min over a temperature range of 450-650 degrees C, and the apparent activation energy for film growth was 0.15 eV. A plot of the E(a) values for deposition from Cl(4)(RCN)W(NR') [R' = Ph, (i)Pr, allyl] against the N-C imido bond strengths for the analogous amines R'NH(2) is linear, implicating cleavage of the N-C bond as the rate-determining step in film growth. The correlation of mass spectral fragmentation patterns for Cl(4)(RCN)W(NR') with film properties such as nitrogen content supports the significance of facile N-C bond cleavage in film growth.

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A variety of rhenium asymmetric π-basic dearomatization agents of the general formula TpRe(CO)(L)(L π ) (Tp ) hydridotris(pyrazolyl)borate; L ) t BuNC, pyridine, PMe 3 , 1-methylimidazole, or NH 3 ; L π ) dihapto-coordinated ligand) have been synthesized via three different routes. By varying the ligand, L, the steric and electronic properties of these complexes can be tuned, and thus the stability and selectivity of the η 2 -aromatic systems can be adjusted. Comparisons among the various rhenium complexes are presented as well as comparisons to the established pentaammineosmium(II) system. Scheme 2. Synthesis of Re(I) η 2 -Aromatic Complexes