Synthesis and coordination compounds of a bis(imino)acenaphthene (BIAN)-supported N-heterocyclic carbene.

The bis(imino)acenaphthene-supported N-heterocyclic carbene IPr(BIAN) has been prepared by deprotonation of the precursor imidazolium chloride. Treatment of IPr(BIAN) imidazolium chloride with Ag(2)O afforded the silver complex [IPr(BIAN)]AgCl which can be converted into the corresponding gold complex [IPr(BIAN)]AuCl by reaction with (tht)AuCl (tht = tetrahydrothiophene). The iridium complex [IPr(BIAN)]Ir(COD)Cl was prepared by reaction of the imidazolium chloride with KO(t)Bu and [Ir(COD)Cl](2) and subsequently converted to the carbonyl complex [IPr(BIAN)]Ir(CO)(2)Cl by exposure to an atmosphere of CO.

The synthesis and characterization of [IMesH](+)[(eta(3)-C(5)H(5))V(N)Cl(2)](-): An anionic vanadium(v) complex with a terminal nitrido ligand.

A series of new half-sandwich vanadium complexes have been prepared. The structures of two new anionic vanadium half-sandwich complexes, [CpVCl(3)](-) and [CpV(N)Cl(2)](-) are presented. (15)N isotopic labelling studies have been conducted to unambiguously assign the V[triple bond, length as m-dash]N infra red stretching frequencies of both a neutral and an anionic (cyclopentadienyl)vanadium nitrido complex.

Intramolecular C-H...Ccarbene hydrogen bonds and competing interactions in monoprotonated tripodal carbenes.

The anionic tripodal N-heterocyclic carbene (C3N2H3)3BH- first prepared by Fehlhammer, together with three neutral variants, (C3N2H3)3CH, (C3N2H3)3P, and (C3N2H3)3SiH, have been studied using quantum chemical methods. Isodesmic reactions are used to deduce that the phosphine-bridgehead species in particular has a large-resonance stabilization energy. All the podands undergo substantial conformational change on excitation to the lowest triplet electronic state, with effective localization of the excitation on one of the heterocyclic rings, dearomatizing it.

Amine elimination synthesis of a titanium(IV) N-heterocyclic carbene complex with short intramolecular Cl...C carbene contacts.

The reaction of 1,3-dimesitylimidazolium chloride with Ti(NMe(2))(4) results in the 1,3-dimesitylimadazol-2-ylidene complex of Ti(NMe(2))(2)Cl(2)(3); the X-ray crystal structure of 3 evidences short intramolecular Cl...

A monomeric imidazol-2-ylidene-silver(I) chloride complex: synthesis, structure, and solid state 109Ag and 13C CP/MAS NMR characterization.

The structure of 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene-silver(I) chloride, 1, has been determined to be a monomer with weak head-to-tail H...

A highly stable N-heterocyclic carbene complex of trichloro-oxo-vanadium(V) displaying novel Cl-Ccarbene bonding interactions.

Reaction of 1,3-dimesitylimidazol-2-ylidene and trichloro-oxo-vanadium(V) yields an air stable 1:1 adduct, which demonstrates the utility of N-heterocyclic carbenes to stabilize metal complexes in high oxidation states. The molecular structure of this compound reveals that the chloride ligands cis to the carbene are oriented toward the Ccarbene atom. Density functional theory calculations show that a bonding interaction occurs between lone pairs of these chlorides and the formally unoccupied p-orbital of the carbene.