CpRu

Bimetallic Complexes. There are two types of bimetaUic organometaUic thorium complexes those with, and those without, metal—metal interactions. Examples of species containing metal—metal bonds are complexes with Ee or Ru carbonyl fragments. Cp ThX(CpRu(CO)2), where X = Cl or 1, and Cp7Th(CpM(CO)2), where M = Ee or Ru, have both been prepared by interaction of CP2TI1X2 or Cp ThCl [62156-90-5] respectively, with the anionic metal carbonyl fragment. These complexes contain very polar metal—metal bonds that can be cleaved by alcohols. 

The TiVS) coordination of thiophene was proposed for [(ri -Cp)Ru(PPh3)2(Ti -C4H4S)]" " prepared from [CpRu(PPh3)2Cl], thiophene, and AgBp4 (76JA689,... 

The reaction of CpRu(CO)2Me with PR3 (R = CgH, or Ph) at 160-180° affords the expected CpRu(CO)(PR3)COMe (101). The temperatures employed are suggestive of the lower reactivity of CpRu(CO)2R than CpFe(CO)2R in the insertion. 

To make 1, [CpRu(CH3CN)3]3 F6 in acetone was allowed to react with 4, forming a mixture of 3d and chelate 1 (10). This mixture could be used but for purposes of catalyst characterization and further testing was converted to > 90% pure 1 by repeated coevaporation of added acetone with the acetonitrile liberated. Complex 1 showed diagnostie NMR data consistent with a chiral stracture and foin unique, diastereotopic methyl groups. 

CpRu(CH3CN)3PF6 catalyzes hydrosilylation of both terminal and internal alkynes. With this catalyst, addition exhibits the opposite regiochemistry. 

The reaction of 4-difluorophosphino-[l,2,3]diazaphosphole 115, even in an excess amount, with CpRu(PPh3)2Cl resulted in the formation of monosubstituted complex CpRu(PPh3)(115)Cl only (Scheme 35). In contrast to the monosubstitution... 

Recently, Bergman and Raymond reported on the stabilization of highly reactive organometallic species inside self-assembled [M4L6] coordination cages (120). The very reactive ion [CpRu(cis-l,3,7-octatriene)]BF4, for example, decomposes rapidly in aqueous solution (within minutes), but is stable for weeks in the same solvent when encapsulated in the tetrahedral [Ga4(L13)6]12- cage... 

CpRu(PPh3)2Cl and the corresponding indenyl complex are effective catalysts for isomerization of a wide range of allylic alcohols.36 37 The reactions proceeded in good yield for a wide range of primary and secondary allylic alcohols using 5% catalyst and 10% Et3NHPF6 in dioxane at 100 °C (Scheme 13). 

Scheme 7 shows that the method of sequential arylation with a high selectivity, using 2-phenylimidazole motif, proves to be applicable for pharmaceuticals and fluorescent and chemiluminescent probes.85 The direct 4-arylation of free 2-phenylimidazole is achieved with iodoarenes as the aryl donors in the presence of palladium catalyst (Pd/PPh3) and MgO as the base. A complete switch from G4 to C2 arylation is accomplished using a ruthenium catalyst [CpRu(PPh3)2Cl] and Gs2G03. 

Dienes such as 90 can be accessed by a multi-component reaction under ruthenium catalysis involving an allene 88 and an enone (methyl vinyl ketone in this case), with cerium(m) chloride as an additive in DMF (Scheme 26).95,96 With an allene concentration of 0.25 M, yields are moderate to good. Different ruthenium catalysts and additives were tested in order to optimize this reaction. CpRu(COD)Cl 89 and CpRu(MeCN)3PF6 appeared to be more versatile ones. The mono-, di-, tri-, and tetrasubstituted allenes have been investigated with methyl vinyl... 

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