59809-88-0Relevant academic research and scientific papers
Formation of carboalkoxyiridium complexes by carbonylation of alkoxyiridium complexes and the crystal structure of trans-PhOIr(CO)(PPh3)2
Rees, Wayne M.,Churchill, Melvyn Rowen,Fettinger, James C.,Atwood, Jim D.
, p. 2179 - 2185 (2008/10/08)
The preparation of iridium alkoxide complexes trans-ROIr(CO)(PPh3)2 and their carbonylation to carboalkoxy complexes ROC(O)Ir(CO)2(PPh3)2 are described for R = Me, n-Pr, t-Bu, and Ph. The preparations involve metathetical reactions between trans-Ir(CO)(PPh3)2Cl and NaOR. In the carbonylation an intermediate can be identified by infrared and conductivity studies as [Ir(CO)3(PPh3)2+][OR-]. Thus a mechanism involving alkoxide displacement by CO and subsequent nucleophilic attack of alkoxide on a CO of the cation is indicated. The complex trans-PhOIr(CO)(PPh3)2 crystallizes in the centrosymmetric monoclinic space group P21/c (no. 14) with a = 15.790 (3) ?, b = 11.461 (3), c = 19.986 (5) ?, β = 100.326 (18)°, V = 3558 (2) ?3, and Z = 4. Diffraction data (Mo Kα, 2θ = 5-55°) were collected with a Syntex P21 automated four-circle diffractometer, and the structure was solved and refined to RF = 6.2% and RwF = 4.6% for all 8220 reflections (RF = 3.8% and RwF = 4.1% for those 5981 reflections with |F0| > 6σ(|F0|)). The iridium atom has the expected square-planar geometry with Ir-P(1) = 2.328 (1) ?, Ir-P(2) = 2.344 (1) ?, Ir-CO = 1.795 (5) ?, and Ir-OPh = 2.049 (4) ?. The phenoxide ligand is "bent" with 〈Ir-O-C(ipso) = 126.5 (3)°.
THE REACTION OF TRIHYDROBISTRIPHENYLPHOSPHINE IRIDIUM IrH3(PPh3)2 WITH DIAZONIUM SALTS
Angoletta, Maria,Caglio, Giorgio
, p. 99 - 106 (2007/10/02)
The reaction of IrH3(PPh3)2 with p-substituted aryldiazonium salts gives the compounds +BF4- at low temperature (-10 deg C) and the o-metalated complexes (R=F, OCH3) at 40-50 deg C.The reactions of the o-metalated complexes with CO, PPh3, NaI and HCl have been studied.
