Iridium ferrocene

It has been reported that a cationic iridium such as [Ir(cod)2]BARF (BARF = 3,5-(CF3)2C6H3 4B), when combined with l,l -bis(diphenylphosphino)ferrocene (DPPF), catalyzed a hydrogen-mediated reductive carbon-carbon bond formation [68]. Thus, the reaction of alkynes 150 with a-ketoesters 151 produces p.y-unsaturated-a-hydroxy ketones 152 (Equation 10.40). 

Cyclometallated iridium complexes, for OLEDs, 12, 145 Cyclometallated palladium(II) complexes from amines and pyridines, 8, 280 with C,C-chelating ligands, 8, 291 enantioselective synthesis, 8, 296 ferrocene-based palladacycles, 8, 292 four-membered palladacycles, 8, 297 imine- and oxime-based complexes, 8, 285 with N-N and N=N bonds, 8, 288 palladacycle catalysis, 8, 297... 

The ferrocene-iridium complexes, analogs of the rhodium complexes illustrated in Scheme 7-26, are shown in Scheme 7-28. 

Phosphines ligands that have chirality from ferrocenes have been implemented in the iridium-catalyzed asymmetric hydrogenation of imine with moderate enantioselectivities for Novartis s manufacture of metolachlor. Electronic modifications of these ferrocenyl ligands have increased the enantioselectivity and catalyst reactivity for Lonza s asymmetric hydrogenation processes of biotin and 2-substituted piperazines, intermediates for several pharmaceutical drugs. 

Complex chemistry of cyclophanes links the two best examined two-layered molecules of organic and organometallic chemistry, namely [22 ]para-cyclophane and ferrocene. The rich redox chemistry of ruthenium, cobalt, rhodium and iridium therefore provides a basis for constructing polymeric structures, of which some oligomeric building units are already known. 

This group includes an important part of organometallic chemistry, that of arene, ferrocene and cymanthrene complexes and certain complexes of rhodium and iridium. In this case the chiral element is composed of the metal and the prochiral ligand. Figure 2.23 represents the two enantiomers of the 1,2-disubstituted ferrocene complex(2.15). ... 

The cationic Rh and Ir complexes with chiral (iminophosphoranyl)ferrocene ligands (107) and (108) were found to be very powerful catalysts for asymmetric hydrogenation of a series of unfunctionalized di- and trisubstituted olefins with almost perfect enantiomeric excesses (up to 99% ee) under mild conditions. In some cases the rhodium complexes were even better catalysts than their iridium counterparts. ... 

C20H28Cr2 ,0P2 f Bis[(Tj -cyclopentadienyl)dicarbonyl(trimethyl phos-phite)chromium](Cr-Cr), 45B, 971 C2oH28FeSi4, 1,1 -Bis(pentamethyldisilanyl)ferrocene, 33B, 353 C2oH3oBr4lr2, Di-M-bromobis[bromo(T -pentamethylcyclopentadienyl)iridium], 45B, 971... 

C2 H2oFe, U)-(1,2-Diphenylethenyl)ferrocene, 45B, 975 C24H2oFe404, Cyclopentadienyliron carbonyl tetramer, 38B, 784 C2 4H20I r Cyclopentadienyl (triphenylphosphine) carbonyl iridium,... 

Also, pincer ligands have been prepared from l,3-bis(diisopropyl or /-butyl)(phosphinomethyl)ruthenocene. Notably, the iridium and rhodium complexes of these have been discussed. The iridium hydride complex [Ir(H)(Cl)[ 2,5-(Bu PCH2)2C5H2 Ru(Cp)]] exists in the form of a mixture of endo- and o-isomers, the exo being the more thermodynamically favorable.Trimetallic ruthenocene/ferrocene ligands 23 have been prepared in three steps from l,l -diacetylruthenocene, and further derivatized to the pentametallic bis-palladium allyl complex 24. 

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