1.5- Cyclooctadiene iridium complexes

C2H,N, Pyridine, 3,5-dimethyl-palladium complex, 26 210 CbHsNO, Benzoyl isocyanide chromium com-C HbO, Ethanone, 1-phenyl-manganese complex, 26 156-158 CBH, 02, Methyl benzoate chromium complex, 26 32 C H i, o-Xylylene magnesium complex, 26 147 ChH P, Phosphine, dimethylphenyl-iron complex, 26 61 ruthenium complex, 26 273 ChH12, 1,5-Cyclooctadiene iridium complex, 26 122 ruthenium complexes, 26 69-72, 253-256 ChH OjPS, 2-Butenedioic acid, 2-(dimethylphosphinothioyl)-dimethyl ester, manganese complex, 26 163... 

C4H,o, 1,3,5-Cyclooctatriene, ruthenium complex, 22 178 CgHl2, 1,5-Cyclooctadiene, iridium complexes, 23 127 rhodium complex, 23 127, 129 ruthenium complex, 22 178 C8H]4, Cyclooctene, iridium complex, 21 102 CsH16, Cyclooctane, boron complex, 22 199... 

CgH,2, 1,5-Cyclooctadiene, iridium complex, 26 122 nickel complex, 28 94 osmium-rhodium complex, 27 29 palladium and platinum complexes, 28 346-348... 

Reaction of the cationic cyclooctadiene iridium complex [Ir( n -COD)(PMe3)3]+[Cl] with carbanions afforded236 different products depending on the nature of the carbanion. For resonance stabilised carbanions (indenyl, allyl, benzyl) the products were (2-substituted cyclooct-5-en-l-yl)tris(trimethylphosphine) complexes derived from nucleophilic attack on one of the coordinated double bonds of the diene. One such complex, [(2-benzylcyclooct-5-en-l-yl)tris(trimethylphosphine)iridium], (19), was characterised by X-ray diffraction. For non-... 

The bridging chloride ligands in these [Ir(olefin)2Cl]2 compounds are susceptible to metathesis reactions, yielding new dimeric compounds of the form [Ir(olefin)2B]2 where B represents a new bridging ligand. AUcoxides, thiolates, and carboxylates have all been employed successfully in the replacement of chloride. The complexes with B = Br, I have also been prepared, both by metathesis reactions and by direct reaction of cyclooctene or cyclooctadiene with IrBrs or Iris The olefin complexes also provide excellent starting materials for the syntheses of arene and cyclopentadienyl iridium complexes, a subject that will be discussed in the next section. 

An NMR study (597) of ligand exchange in the system (diene)MCl(L) (diene = norbornadiene or 1,5-cyclooctadiene M = Rh or Ir L = tertiary phosphine, arsine, or stibene) shows a first-order dependence of the rate upon both L and the olefin complex in the temperature range from —70° to —10°C. The exchange involves an 8 2 mechanism with the five-coordinate complex (diene)MCl(L)2 as intermediate. The intermediate iridium complexes (l,5-CgHi2)IrCl(L)2 can be isolated from ethanolic solution. The activation energy for the process ranges from 4 to 10 kcal/mole (597). 

The effect of added iodide on the addition of CH3I to an iridium complex, [Ir(cod)(o-phen)] Cl (cod = cyclooctadiene), was investigated ... 

In contrast, the iridium complex XLVb is more reactive than the corresponding rhodium complex XLVa. Furthermore, the reaction rates in this reaction are independent of the diene (cyclooctadiene isoprene 2,3-dimethylbutadiene) . 

Hydrogen transfer reactions are catalyzed by several iridium complexes, including the dimethyl sulfoxide (DMSO) complexes cis- and trans-[Ir(Cl)4(DMSO)2]", [Ir(Cl)3(DMSO)3] and [lr(H)-(Cl)2(DMSO)3], as well as the cyclooctadiene (cod) complexes [Ir(Cl)(cod)]2 and [Ir(3,4,7,8-Me4phen)(cod)], and tra 5-[Ir(Cl)(CO)(PPh3)2]. Vaska s complex catalyzes the conversion of p-methoxybenzoyl chloride to the corresponding aldehyde. The dimethyl sulfoxide iridium(III) complexes catalyze hydrogen transfer from propan-2-ol to unhindered cyclohexanones to yield cyclohexanols, while the cod complexes serve as catalysts in the transfer of hydrogen from propan-2-ol to alkenes, ketones and a,/3-unsaturated ketones. ... 

Dimethyl H-phosphonate oxidatively adds to Ir (I) and Rh (I) compounds with the formation of hydrido-fr(ni) and hydrido-Rh(lII) phosphonato complexes [439]. Treatment of chloro-bis(cyclooctadiene) iridium (I) [IrCl(C8Hj4)2]2 with two equivalents of triphenyl phosphine and subsequent reaction with dimethyl H-phosphonate affords two products of oxidative addition I and II, which have not been spectroscopically distinguished ... 

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