Iridium complexes mononuclear

Organometallic Compounds. The predominant oxidation states of indium in organometalUcs are +1 and +3. Iridium forms mononuclear and polynuclear carbonyl complexes including [IrCl(P(C3H3)3)2(CO)2] [14871-41-1], [Ir2014(00)2] [12703-90-1], [Ir4(CO)22] [18827-81 -1], and the conducting, polymeric [IrCl(CO)3] [32594-40-4]. Isonitnle and carbene complexes are also known. 

Deprotonation with aluminum alkys, 9, 272 mononuclear carbonyl iridium complexes, 7, 302 for palladium cyclopentadienyl complexes, 8, 390 in Ru and Os half-sandwich preparations, 6, 569 in silver carbene synthesis, 2, 206 Desulfurization... 

Mel, in Rh-catalyzed methanol carbonylation, 7, 256 to monocarbonyl iridium complexes, 7, 284 in mononuclear ruthenium and osmium alkynyl formations,... 

The rhodium(l) complexes were yellow/orange in the solid state, which is characteristic of mononuclear Rh(l), whereas the iridium(l) complexes were burgundy in the solid state and yellow in isotropic solution or in the melt. Infrared spectra suggested that the iridium complexes were associated in some way in the solid state, possibly in a... 

See the general references in the Introdnction, specifically [116], [121] and [313], and some more-specialized books [2-5], Some articles in journals discuss DF theory for [Rli6(PH3)6Hm] , m = 12, 14 or 16 [6] reductions of Co by metallic ions [7] iridium [8] mononuclear cyanocobalt(lll) complexes [9] Ii chloro and bromo species [10] and metal-metal bonding in Rh [11],... 

The rhodium complexes were yellow/ orange in the solid state characteristic of mononuclear Rh(I), while the burgundy iridium complexes became yellow both in solution and on melting. Both series of materials showed very similar mesomorphism nematic phases were found at short chain lengths giving way to the SmA phase for higher homologues for the two metals [20]. 

Non-ionic thiourea derivatives have been used as ligands for metal complexes [63,64] as well as anionic thioureas and, in both cases, coordination in metal clusters has also been described [65,66]. Examples of mononuclear complexes of simple alkyl- or aryl-substituted thiourea monoanions, containing N,S-chelating ligands (Scheme 11), have been reported for rhodium(III) [67,68], iridium and many other transition metals, such as chromium(III), technetium(III), rhenium(V), aluminium, ruthenium, osmium, platinum [69] and palladium [70]. Many complexes with N,S-chelating monothioureas were prepared with two triphenylphosphines as substituents. 

The most fundamental reaction is the alkylation of benzene with ethene.38,38a-38c Arylation of inactivated alkenes with inactivated arenes proceeds with the aid of a binuclear Ir(m) catalyst, [Ir(/x-acac-0,0,C3)(acac-0,0)(acac-C3)]2, to afford anti-Markovnikov hydroarylation products (Equation (33)). The iridium-catalyzed reaction of benzene with ethene at 180 °G for 3 h gives ethylbenzene (TN = 455, TOF = 0.0421 s 1). The reaction of benzene with propene leads to the formation of /z-propylbenzene and isopropylbenzene in 61% and 39% selectivities (TN = 13, TOF = 0.0110s-1). The catalytic reaction of the dinuclear Ir complex is shown to proceed via the formation of a mononuclear bis-acac-0,0 phenyl-Ir(m) species.388 The interesting aspect is the lack of /3-hydride elimination from the aryliridium intermediates giving the olefinic products. The reaction of substituted arenes with olefins provides a mixture of regioisomers. For example, the reaction of toluene with ethene affords m- and />-isomers in 63% and 37% selectivity, respectively. 

Alkyl-2-phenyl-5(4//)-oxazolones 342 react with the chloro-bridged iridium(III) complex [(t -C5Me5)IrCl2]2 to give cyclometalated mononuclear complexes 343. 

A number of iridium-porphyrin systems, including mononuclear and cofacial diporphyrins, have been adsorbed on pyrolytic edge-plane graphite electrodes and tested for their ability to reduce dioxygen to water (82). The original system investigated, [Ir(oep)H], where oep = 2,3,7,8,12,13,17,18-octaethylprophyrinato, was unique in that, while monomeric, the complex was still active in acidic solutions at potentials of +0.72 V vs NHE at pH 1 (82a). The [Ir(oep)H] did become inactive at potentials less than +0.2 V vs NHE, unlike the cofacial dicobalt diporphyrin systems. In the more recent report of these systems (82b),... 

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