Mono complexes iridium

A special type of reaction is observed with the platinum(IV) complex [PtI(Me)3] which cleaves the Af,N,Af, A -tetraphenyltetraaminoethylene under reduction to form the dimeric cyclometallated mono(NHC) complex of platinum(II) iodide [Eq. (31)]. Cyclometallation with the same ligand is also observed for ruthe-nium. Additional cyclometallations with various substituents of NHCs have been reported for ruthenium(II), rhodium(III), iridium(I), palladium(II), " and platinum(II). In the case of iridium, alkyl groups can be activated twice. In rare cases like for nickel(II) /x-bridging NHCs have been obtained. ... 

IX. Equilibria between Mono- and Dihydroxo-Bridged Dinuclear Complexes of Chromium(III), Rhodium(III), and Iridium(III)... 

Imidazolium ligands, in Rh complexes, 7, 126 Imidazolium salts iridium binding, 7, 349 in silver(I) carbene synthesis, 2, 206 Imidazol-2-ylidene carbenes, with tungsten carbonyls, 5, 678 (Imidazol-2-ylidene)gold(I) complexes, preparation, 2, 289 Imidazopyridine, in trinuclear Ru and Os clusters, 6, 727 Imidazo[l,2-a]-pyridines, iodo-substituted, in Grignard reagent preparation, 9, 37—38 Imido alkyl complexes, with tantalum, 5, 118—120 Imido-amido half-sandwich compounds, with tantalum, 5,183 /13-Imido clusters, with trinuclear Ru clusters, 6, 733 Imido complexes with bis-Gp Ti, 4, 579 with monoalkyl Ti(IV), 4, 336 with mono-Gp Ti(IV), 4, 419 with Ru half-sandwiches, 6, 519—520 with tantalum, 5, 110 with titanium(IV) dialkyls, 4, 352 with titanocenes, 4, 566 with tungsten... 

Pentamethylcyclopentadienyl complexes CpjAnX, 4, 207 Cp AnX2 and Cp AnX, 4, 206 Cp MX compounds, 4, 62 with iridium amidinates, 7, 366 mono(Cp ) actinide(IV) compounds, 4, 207 with Ni-C cr-bonded ligands, 8, 108-109 with rhodium, 7, 152 with ruthenium, 6, 632 tris(Cp ) actinide(IV) compounds, 4, 219 with zirconium amidinates, 12, 730 l, 2, 3, 4, 5 -Pentamethyl-l-formylruthenocene, preparation, 6, 643... 

In addition to ruthenium, Tilley and coworkers also reported that cationic iridium silylenoid complexes were efficient olefin hydrosilation catalysts [reaction (7.6)].56 This silylene complex catalyzes the hydrosilation of unhindered mono- or disubsti-tuted olefins with primary silanes to produce secondary silanes with anti Markovni-kov selectivity. Iridium catalyst 32 exhibited reactivity patterns similar to those of ruthenium 30 only primary silanes were allowed as substrates. In contrast to 30, cationic iridium 32 catalyzed the redistribution of silanes. Exposing phenylsilane to 5 mol% of 32 in the absence of olefin produced diphenylsilane, phenylsilane, and silane. 

Several mononuclear carbonyl complexes may be synthesized with iridium(I), but most intriguing of those are the binary carbonyls. [Ir(CO)4] (46) may be synthesized by the reduction of Ir4(CO)i2 (45) with sodium under an atmosphere of carbon monoxide. More vigorous reduction of (45) with sodium can also yield the very reactive trianion, [Ir(CO)3] (47) (equation 13). These anions may then be used for the synthesis of other mono and polynuclear (see Polynuclear Complexes) carbonyl compounds of iridium. 

Perhaps as a consequence of Johnson s failure, 20 years elapsed before Sessler and coworkers reported that certain p -type complexes could in fact be formed with heterosapphyrins.These latter workers were clearly inspired by their earlier successful syntheses of p -type rhodium(I) and iridium(I) carbonyl complexes of pentaazasapphyrins 5.21 and 5.23 vide supra). Thus, in a first experiment, they treated the monothiasapphyrin 5.71 with Rli2(CO)4Cl2 (Scheme 5.5.4). This afforded the structurally characterized [Rh(CO)2]2 monothiasapphyrin complex 5.100 (Figure 5.5.6). Subsequently, they prepared the bis-iridium complex 5.101 of the mono-selenasapphyrin 5.73. This complex was also characterized by X-ray diffraction analysis. The resulting structure then served to confirm the expected sitting-a-top binding mode (Figure 5.5.7). 

Pyridazine forms a stable adduct with iodine, with semiconductor properties. " Similar complexes were prepared from iodine mono-ehloride, bromine, and nickel(II) ethyl xanthate. Complexes of pyrida-zines with iron carbonyls and with iron carbonyls and triphenylphosphine have been prepared and investigated. " Complexes of pyridazines with boron trihalides, silver salts, mercury(I) salts, iridium salts, " ruthenium salts, and chromium carbonyls are re-... 

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