33394-10-4Relevant articles and documents
Oxidative addition and reductive elimination reactions of trans-[Ir(PPh3)2(CO)(NC4H4)] and trans,cis-[Ir(PPh3)2(H)2(CO)(NC 4H4)], including N-H bond-forming reductive elimination of pyrrole
Driver, Michael S.,Hartwig, John F.
, p. 1134 - 1143 (2008/10/08)
The complex trans-(PPh3)2(CO)Ir(NC4H4) (1) has been synthesized and is an analogue of metal-aryl complexes, but with a nitrogen of the heteroaromatic group covalently bonded to the transition metal. Compound 1 readily undergoes initial reaction with a variety of substrates at the metal center rather than at the pyrrolyl nitrogen, allowing for the study of reactions between the pyrrolyl group and accompanying covalent ligands. These reactions ultimately produce N-substituted pyrroles, X-NC4H4 (X = C(O)CH3, C(O)C6H4CH3, H, SnMe3, SiMe3, SiEt3, Bcat). Compound 1 undergoes oxidative addition of H2 to form the stable Ir-(III) product (PPh3)2(CO)Ir(H)2(NC4H4) (2). When pure 2 is heated, it undergoes simple elimination of H2 to regenerate 1; however, if 2 is heated for longer times under H2 in the presence of PPh3, it undergoes reductive elimination of pyrrole and forms (PPh3)3(CO)Ir(H). Qualitative analysis of the mechanism of this reaction suggests that it occurs by either direct reductive elimination from the octahedral complex or rate-determining ligand dissociation, followed by rapid reductive elimination of pyrrole. Reductive elimination of pyrrole from 2 was also observed to occur photochemically by initial irreversible dissociation of a dative ligand.
Selectivity in C-O bond formation: Reaction of acid chlorides and methyl iodide with trans-MeOIr(CO)(PPh3)2
Bernard, Karen A.,Atwood, Jim D.
, p. 1133 - 1134 (2008/10/08)
Reactions of RX (RX = MeI, CH3C(O)Cl, C6H5C(O)Cl, and C6H5CH2C(O)Cl) with trans-MeOIr(CO)(PPh3)2 have been examined. In each case, an adduct is formed, RIr(OMe)(CO)(PPh3)2X, which is stable for R = Me. For the acid chlorides, this adduct eliminates ester, forming Ir(CO)(PPh3)2Cl. Thus the carbon-oxygen bond leading to ester products is formed more readily than the carbon-oxygen bond leading to dimethyl ether.