CpIr(dab) (dab = 1,4-Bis(2,6-dimethylphenyl)-1,4-diazabutadiene):  A Coordinatively Unsaturated Six-π-Electron Metallaheteroaromatic Compound?

CpIr(dab) (dab = 1,4-Bis(2,6-dimethylphenyl)-1,4-diazabutadiene):  A Coordinatively Unsaturated Six-π-Electron Metallaheteroaromatic Compound?

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) Å, b = 15.823(2) Å, c = 11.677(1) Å, V = 2990.8(6) Å3, Z = 4, and R = 0.0588. On reaction with NaBH...

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Veröffentlicht in:Inorganic chemistry 1996-06, Vol.35 (13), p.3998-4002
Hauptverfasser: Greulich, Stefan, Kaim, Wolfgang, Stange, Andreas F, Stoll, Hermann, Fiedler, Jan, Záliš, Stanislav
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container_end_page 4002
container_issue 13
container_start_page 3998
container_title Inorganic chemistry
container_volume 35
creator Greulich, Stefan
Kaim, Wolfgang
Stange, Andreas F
Stoll, Hermann
Fiedler, Jan
Záliš, Stanislav
description 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) Å, b = 15.823(2) Å, c = 11.677(1) Å, V = 2990.8(6) Å3, Z = 4, and R = 0.0588. On reaction with NaBH3CN this compound does not form an iridium(III) hydride but the coordinatively unsaturated reduced product Cp*Ir(dab):  C28H35IrN2, monoclinic, space group P21/n, a = 8.484(2) Å, b = 14.535(3) Å, c = 20.956(4) Å, β = 98.88(3)°, V = 2553.2(9) Å3, Z = 4, and R = 0.0586. The inverted relation d CC (=1.334(15) Å) < d CN (=1.379(13) and 1.366(14) Å) in the dab ligand of Cp*Ir(dab) suggests that the reduction has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-π-electron metallaheteroaromatic system. Ab initio pseudopotential calculations of model complexes [CpIr(HNCHCHNH)]0/2+ support this description of the bonding.
doi_str_mv 10.1021/ic9514814
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On reaction with NaBH3CN this compound does not form an iridium(III) hydride but the coordinatively unsaturated reduced product Cp*Ir(dab):  C28H35IrN2, monoclinic, space group P21/n, a = 8.484(2) Å, b = 14.535(3) Å, c = 20.956(4) Å, β = 98.88(3)°, V = 2553.2(9) Å3, Z = 4, and R = 0.0586. The inverted relation d CC (=1.334(15) Å) &lt; d CN (=1.379(13) and 1.366(14) Å) in the dab ligand of Cp*Ir(dab) suggests that the reduction has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-π-electron metallaheteroaromatic system. 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Chem</addtitle><description>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) Å, b = 15.823(2) Å, c = 11.677(1) Å, V = 2990.8(6) Å3, Z = 4, and R = 0.0588. On reaction with NaBH3CN this compound does not form an iridium(III) hydride but the coordinatively unsaturated reduced product Cp*Ir(dab):  C28H35IrN2, monoclinic, space group P21/n, a = 8.484(2) Å, b = 14.535(3) Å, c = 20.956(4) Å, β = 98.88(3)°, V = 2553.2(9) Å3, Z = 4, and R = 0.0586. The inverted relation d CC (=1.334(15) Å) &lt; d CN (=1.379(13) and 1.366(14) Å) in the dab ligand of Cp*Ir(dab) suggests that the reduction has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-π-electron metallaheteroaromatic system. 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Chem</addtitle><date>1996-06-19</date><risdate>1996</risdate><volume>35</volume><issue>13</issue><spage>3998</spage><epage>4002</epage><pages>3998-4002</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><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) Å, b = 15.823(2) Å, c = 11.677(1) Å, V = 2990.8(6) Å3, Z = 4, and R = 0.0588. On reaction with NaBH3CN this compound does not form an iridium(III) hydride but the coordinatively unsaturated reduced product Cp*Ir(dab):  C28H35IrN2, monoclinic, space group P21/n, a = 8.484(2) Å, b = 14.535(3) Å, c = 20.956(4) Å, β = 98.88(3)°, V = 2553.2(9) Å3, Z = 4, and R = 0.0586. The inverted relation d CC (=1.334(15) Å) &lt; d CN (=1.379(13) and 1.366(14) Å) in the dab ligand of Cp*Ir(dab) suggests that the reduction has occurred primarily at that ligand to form an ene-1,2-diamido/iridium(III) moiety or, alternatively, a six-π-electron metallaheteroaromatic system. Ab initio pseudopotential calculations of model complexes [CpIr(HNCHCHNH)]0/2+ support this description of the bonding.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>11666595</pmid><doi>10.1021/ic9514814</doi><tpages>5</tpages></addata></record>
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title CpIr(dab) (dab = 1,4-Bis(2,6-dimethylphenyl)-1,4-diazabutadiene):  A Coordinatively Unsaturated Six-π-Electron Metallaheteroaromatic Compound?
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