Silica-supported oxovanadium groups were reacted in a gas-solid reaction with aniline at 175 degrees C. The reaction was clean as monitored in situ by UV-vis spectroscopy and resulted in the elimination of water as the principal product of the reaction and the disappearance of the terminal V=O stretch in the Raman spectrum. 15N MAS solid-state NMR spectroscopy showed only a single nitrogen-cont...

The mononuclear, five-coordinate organochromium(V) compound [NBu(4)][CrO(C(6)F(5))(4)] (1) has been obtained as a dark red solid in moderate yield by treatment of the homoleptic organochromium(III) derivative [NBu(4)](2)[Cr(C(6)F(5))(5)] with NO[BF(4)] in CH(2)Cl(2) solution under an oxygen atmosphere. The Cr(V) centre in the [CrO(C(6)F(5))(4)](-) anion shows a square-pyramidal geometry with th...

Uranyl ions, {UO2}n+ (n = 1, 2), display trans, strongly covalent, and chemically robust U-O multiple bonds, where 6d, 5f, 6p orbitals play important roles. The synthesis of isoelectronic analogues uranyl has been interest for quite some time, mainly with the purpose unveiling covalence 5f-orbital participation in bonding. Significant advances have occurred last two decades, initially marked by...

Addition of organic azides, N(3)R (R = 2,4,6-trimethylphenyl (Mes), phenyl (Ph), 1-adamantyl (Ad)), to a solution of the uranium(III) alkyl complex, Tp*(2)U(CH(2)Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) (1), results in the formation of a family of uranium(iv) imido derivatives, Tp*(2)U(NR) (2-R). Notably, these complexes were synthesized in high yields by coupling of the benzyl groups...

In the title complex, [(C(4)H(9))(4)N](2)[Mo(6)O(18)(C(9)H(9)NO(2))]·0.5C(4)H(10)O, the aryl-imido ligand is linked to an Mo atom of the Lindqvist-type polyoxidometalate anion by an Mo N bond of 1.726 (4) Å. The Mo N-C angles are 160.7 (5) and 167.6(5)° because of disorder affecting the aryl group, and is typical for the imido monodentate behaviour described in analogous hybrids. Light componen...

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 ...

An eight-membered thorium(IV) tetraazamacrocycle is produced by the sequential, metal-mediated coupling of four equivalents of 4-fluorobenzonitrile; its formation is consistent with the involvement of an imido intermediate, generated from a thorium ketimide complex.

A terpyridine ligand is covalently linked to a hexamolybdate cluster through the Mo-N imido bond, paving the way for the preparation of hybrids containing covalently bonded transition metal complexes and polyoxometalate clusters.