%0 Journal Article %1 Greulich.1996 %A Greulich, Stefan %A Kaim, Wolfgang %A Stange, Andreas F. %A Stoll, Hermann %A Fiedler, Jan %A Zalis, Stanislav. %D 1996 %J Inorganic Chemistry %K MO ab complex complex;crystal complex;cyclic complex;diazabutadiene cyclopentadienyl diazabutadiene initio iridium pentamethylcyclopentadienyl prepn structure structure;mol voltammetry %N 13 %P 3998--4002 %R 10.1021/IC9514814 %T CpIr(dab) (dab = 1,4-Bis(2,6-dimethylphenyl)-1,4-diazabutadiene): A Coordinatively Unsaturated Six-p-Electron Metallaheteroaromatic Compound? %V 35 %X 1,4-Bis(2,6-dimethylphenyl)-1,4-diaza-1,3-butadiene (dab) forms the structurally characterized iridium(III) complex [Cp*IrCl(dab)](PF6): C28H35ClF6IrN2P, orthorhombic, space group Pnma, a = 16.187(2) \AA, b = 15.823(2) \AA, c = 11.677(1) \AA, V = 2990.8(6) \AA3, Z = 4, and R = 0.0588. On reaction with NaBH3CN this compd. does not form an iridium(III) hydride but the coordinatively unsatd. reduced product Cp*Ir(dab): C28H35IrN2, monoclinic, space group P21/n, a = 8.484(2) \AA, b = 14.535(3) \AA, c = 20.956(4) \AA, b = 98.88(3)°, V = 2553.2(9) \AA3, Z = 4, and R = 0.0586. The inverted relation dCC (=1.334(15) \AA) \textless dCN (=1.379(13) and 1.366(14) \AA) in the dab ligand of Cp*Ir(dab) suggests that the redn. has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-p-electron metallaheteroarom. system. Ab initio pseudopotential calcns. of model complexes [CpIr(HNCHCHNH)]0/2+ support this description of the bonding. [on SciFinder(R)]

@article{Greulich.1996, abstract = {1,4-Bis(2,6-dimethylphenyl)-1,4-diaza-1,3-butadiene (dab) forms the structurally characterized iridium(III) complex [Cp*IrCl(dab)](PF6): C28H35ClF6IrN2P, orthorhombic, space group Pnma, a = 16.187(2) {\AA}, b = 15.823(2) {\AA}, c = 11.677(1) {\AA}, V = 2990.8(6) {\AA}3, Z = 4, and R = 0.0588. On reaction with NaBH3CN this compd. does not form an iridium(III) hydride but the coordinatively unsatd. reduced product Cp*Ir(dab): C28H35IrN2, monoclinic, space group P21/n, a = 8.484(2) {\AA}, b = 14.535(3) {\AA}, c = 20.956(4) {\AA}, \textgreek{b} = 98.88(3)°, V = 2553.2(9) {\AA}3, Z = 4, and R = 0.0586. The inverted relation dCC (=1.334(15) {\AA}) {\textless} dCN (=1.379(13) and 1.366(14) {\AA}) in the dab ligand of Cp*Ir(dab) suggests that the redn. has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-\textgreek{p}-electron metallaheteroarom. system. Ab initio pseudopotential calcns. of model complexes [CpIr(HNCHCHNH)]0/2+ support this description of the bonding. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Greulich, Stefan and Kaim, Wolfgang and Stange, Andreas F. and Stoll, Hermann and Fiedler, Jan and Zalis, Stanislav.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2bbbc7fad7bbe154bc7fd611b6d72de17/huebleriac}, doi = {10.1021/IC9514814}, interhash = {d87898452c9d66e2bcdf058d4a754831}, intrahash = {bbbc7fad7bbe154bc7fd611b6d72de17}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {MO ab complex complex;crystal complex;cyclic complex;diazabutadiene cyclopentadienyl diazabutadiene initio iridium pentamethylcyclopentadienyl prepn structure structure;mol voltammetry}, number = 13, pages = {3998--4002}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {CpIr(dab) (dab = 1,4-Bis(2,6-dimethylphenyl)-1,4-diazabutadiene): A Coordinatively Unsaturated Six-\textgreek{p}-Electron Metallaheteroaromatic Compound?}, volume = 35, year = 1996 }