Iridium complexes reactions

Ferrocenoylamino acids have been converted into 2-ferrocenyl-5(477)-oxazo-lones 348 and 350 that act as N donors in palladium, platinum, and iridium complexes. Reaction of 348 with chloro-bridged palladium(II) and platinum(II) complexes affords a series of N-coordinated oxazolone complexes 349. Reaction of the unsubstituted 2-ferrocenyl-5(477)-oxazolone 350 with the chloro-bridged iridium(III) complex [(ri -C5Me5)IrCl2]2 produces a dinuclear complex 351, analogous to that obtained from 2-phenyl-5(477)-oxazolone (Scheme 7.113)." ° ... 

Alkylidene carbonyl iridium complexes, reactions, 7, 275 Alkylidene compounds, NLO properties, 12, 121 Alkylidene-containing complexes, in molybdenum complexes, Schrock-type complexes, 5, 524 a-Alkylidene cyclic carbonyl compounds, isomerization,... 

Reaction of the cyclopentadienyl rhodium and iridium tris(acetone) complexes with indole leads to the species 118 (M = Rh, Ir) [77JCS(D)1654 79JCS(D)1531]. None of these compounds deprotonates easily in acetone, but the iridium complex loses a proton in reaction with bases (Na2C03 in water, r-BuOK in acetone) to form the ri -indolyl complex 119. This reaction is easily reversed in the presence of small amounts of trifluoroacetic acid. 

The five-coordinate iridium complexes may be protonated by glacial acetic acid, yielding [Ir(PPh3)2(CNR)3H] + the structure of this complex is determined by PMR measurements to be (XXIX). However, in the analogous HCl reaction [Ir(PPh3)2(CNR)2Cl2] is obtained. The reaction of [Ir(PPh3)2(CNR)3] with methanol also proved quite out of the ordinary. 

The three iridium complexes 72d, 72f and 72g were analyzed by X-ray diffraction. Unfortunately the iridium complex 72a, the most efficient in many reactions, failed to give suitable crystals for analysis but the corresponding crystalline rhodiiun complex 73 coifld be analyzed. According to the results obtained, the coordination sphere of the Ir atom and of the Rh atom can be described as pseudo-square planar (Fig. 12). 

In 2004, Bolm et al. reported the use of chiral iridium complexes with chelating phosphinyl-imidazolylidene ligands in asymmetric hydrogenation of functionalized and simple alkenes with up to 89% ee [17]. These complexes were synthesized from the planar chiral [2.2]paracyclophane-based imida-zolium salts 74a-c with an imidazolylidenyl and a diphenylphosphino substituent in pseudo ortho positions of the [2.2]paracyclophane (Scheme 48). Treatment of 74a-c with t-BuOLi or t-BuOK in THF and subsequent reaction of the in situ formed carbenes with [Ir(cod)Cl]2 followed by anion exchange with NaBARF afforded complexes (Rp)-75a-c in 54-91% yield. The chela-... 

Schemes 6-13 Reaction of the cationic iridium complex 67 with carboxylic acids...

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