TY - JOUR
T1 - Oxidative Addition of O-H Bonds to Iridium(I)
T2 - Synthesis and Characterization of (Phenolato)- and (Carboxylato)iridium(III) Hydride Complexes
AU - Ladipo, Folami T.
AU - Kooti, Mahimid
AU - Merola, Joseph S.
PY - 1993
Y1 - 1993
N2 - The reactions of alcohols, phenols, and carboxylic acids with [Ir(COD)(PMe3)3]Cl are described. Primary and secondary alcohols react with [Ir(COD) (PMe3)3]Cl to form a complex mixture of hydrido- and carbonylhydridoiridium-(III) compounds. The tertiary alcohol tert-butyl alcohol reacts with [Ir(COD)(PMe3)3]Cl to form isobutylene and the iridium(III) product resulting from oxidative addition of H2O. Phenols react with [Ir(COD)(PMe3)3]Cl to yield octahedral iridium(III) compounds of the form mer-(Me3P)3Ir(OAr)(H)(Cl). One such compound (Ar = 2,4-dimethylphenyl) was crystallographically characterized and was found to belong to the orthorhombic space group Pbcn with a = 13.804(2) Å, b = 16.517(2) Å, c = 22.386(4) Å, V = 5104.0(15) Å3, and Z = 2. Refinement of 226 least-squares parameters for 3404 reflections (F > 4σ(F)) led to final R = 0.0425. The Ir—O distance is 2.109(5) Å, and the Ir—O—C angle is 130.4(5)°. One molecule of dichloromethane per two molecules of iridium complex was found in the crystal lattice apparently with C—H⋯Cl hydrogen bonds formed between the dichloromethane and the chloride of mer-(Me3P)3Ir(OAr)(H)(Cl). Carboxylic acids also react with [Ir(COD)(PMe3)3]Cl to yield octahedral iridium(III) compounds with the resulting complexes of the form mer-(Me3P)3Ir(OC(O)R)(H)(Cl). Crystals of the (benzoato)iridium hydride complex were found to belong to the orthorhombic space group P212121 with a = 10.356(3) Å, b = 11.734 Å, c = 19.561(5) Å, V = 2377(1) Å3, and Z = 4. The Ir—O distance was found to be 2.123(7) Å. Crystals of the (salicylato)iridium hydride compound were found to crystallize in the orthorhombic space group Pbca with a = 12.508(5) Å, b = 13.663(3) Å, c = 27.502(6) Å, V = 4700(2) Å3, and Z = 8. The Ir—O distance was found to be 2.131(6) Å. The structural parameters for these compounds are discussed in terms of the bonding that occurs between iridium(III) and oxygen donor ligands.
AB - The reactions of alcohols, phenols, and carboxylic acids with [Ir(COD)(PMe3)3]Cl are described. Primary and secondary alcohols react with [Ir(COD) (PMe3)3]Cl to form a complex mixture of hydrido- and carbonylhydridoiridium-(III) compounds. The tertiary alcohol tert-butyl alcohol reacts with [Ir(COD)(PMe3)3]Cl to form isobutylene and the iridium(III) product resulting from oxidative addition of H2O. Phenols react with [Ir(COD)(PMe3)3]Cl to yield octahedral iridium(III) compounds of the form mer-(Me3P)3Ir(OAr)(H)(Cl). One such compound (Ar = 2,4-dimethylphenyl) was crystallographically characterized and was found to belong to the orthorhombic space group Pbcn with a = 13.804(2) Å, b = 16.517(2) Å, c = 22.386(4) Å, V = 5104.0(15) Å3, and Z = 2. Refinement of 226 least-squares parameters for 3404 reflections (F > 4σ(F)) led to final R = 0.0425. The Ir—O distance is 2.109(5) Å, and the Ir—O—C angle is 130.4(5)°. One molecule of dichloromethane per two molecules of iridium complex was found in the crystal lattice apparently with C—H⋯Cl hydrogen bonds formed between the dichloromethane and the chloride of mer-(Me3P)3Ir(OAr)(H)(Cl). Carboxylic acids also react with [Ir(COD)(PMe3)3]Cl to yield octahedral iridium(III) compounds with the resulting complexes of the form mer-(Me3P)3Ir(OC(O)R)(H)(Cl). Crystals of the (benzoato)iridium hydride complex were found to belong to the orthorhombic space group P212121 with a = 10.356(3) Å, b = 11.734 Å, c = 19.561(5) Å, V = 2377(1) Å3, and Z = 4. The Ir—O distance was found to be 2.123(7) Å. Crystals of the (salicylato)iridium hydride compound were found to crystallize in the orthorhombic space group Pbca with a = 12.508(5) Å, b = 13.663(3) Å, c = 27.502(6) Å, V = 4700(2) Å3, and Z = 8. The Ir—O distance was found to be 2.131(6) Å. The structural parameters for these compounds are discussed in terms of the bonding that occurs between iridium(III) and oxygen donor ligands.
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U2 - 10.1021/ic00061a025
DO - 10.1021/ic00061a025
M3 - Article
AN - SCOPUS:0000526366
SN - 0020-1669
VL - 32
SP - 1681
EP - 1688
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 9
ER -