148424-90-2Relevant academic research and scientific papers
Oxidative addition of O-H bonds to iridium(I): Synthesis and characterization of (phenolato)-and (carboxylato)iridium(III) hydride complexes
Ladipo, Folami T.,Kooti, Mahimid,Merola, Joseph S.
, p. 1681 - 1688 (2008/10/08)
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) ?, b = 16.517(2) ?, c = 22.386(4) ?, V = 5104.0(15) ?3, 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) ?, 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) ?, b = 11.734 ?, c = 19.561(5) ?, V = 2377(1) ?3, and Z = 4. The Ir-O distance was found to be 2.123(7) ?. Crystals of the (salicylato)iridium hydride compound were found to crystallize in the orthorhombic space group Pbca with a = 12.508(5) ?, b = 13.663(3) ?, c = 27.502(6) ?, V = 4700(2) ?3, and Z = 8. The Ir-O distance was found to be 2.131(6) ?. The structural parameters for these compounds are discussed in terms of the bonding that occurs between iridium(III) and oxygen donor ligands.
