Indenyl complexes

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). 

A ruthenium(n)-indenyl complex, which is an efficient catalyst for the isomerization of allylic alcohols, is also an effective catalyst for the isomerization of propargylic alcohols to both a,/3-enals and a,/ -enones (Scheme 57).96 In this reaction, the addition of 20—40 mol% InClj is highly effective. The reaction exhibits extraordinary chemoselectivity and a variety of functional groups are unaffected, which allows a highly efficient synthesis of dienals (R1 =Me2C = CH, R2 = H). 

Most of the chemistry performed on orthometallated ylides has been carried out with Pd and Pt as metal centers. Few examples dealing with other metals (Co, Ru, and Os mainly, see 62 and 63) have been reported. Complex (74) has been prepared by reaction of a Ru-vinylidene with PPh3 [153] while Os derivative (75) has been obtained after treatment of the methylimido complex with PPh3 [154]. Orthoruthe-nated indenyl complexes [155] have been synthesized by reaction of the halomethyl precursors with PPh3, and the oxidative addition of the yUde Ph3P=CHC(0)H to clusters of Ru and/or Os also allows the synthesis of orthometallated complexes... 

It is noteworthy that the indenyl complex RuCl(ri -C9H7)(PPh3)2l4 provides an efficient catalyst precursor for the anti-Markovnikov hydration of terminal alkynes in aqueous media, especially in micellar solutions with either anionic (sodium dode-cylsulfate (SDS)) or cationic (hexadecyltrimethylammonium bromide (CTAB)) surfactants [38]. This system can be applied to the hydration of propargylic alcohols to selectively produce P-hydroxyaldehydes, whereas RuCl(Cp)(PMe3)2 gives a,P-unsat-urated aldehydes (the Meyer Schuster rearrangement products)(Scheme 10.8) [39]. 

In an attempt to assess the relative cr-donating/n-accepting ability of OFCOT toward Rh(I), these methods have been applied to the indenyl complex 73 (757). 

Bis (indenyl) complexes, with Zr(IV), 4, 935 Bis(indenyl)dimethyl metallocenes, synthesis, 4, 884-885 Bis(indenyl)zirconium sandwich complexes, preparation and reactivity, 4, 728... 

Germanium-bridged complexes, with Zr(IV) and Hf(IV) cyclopentadienyl complexes, 4, 967 fluorenyl complexes, 4, 974 indenyl complexes, 4, 972... 

Indanes, chromium tricarbonyl complexes, 5, 246 Indazoles, in copper-catalyzed lead reactions, 9, 409 Indenes, chromium tricarbonyl complexes, 5, 246 Indenide derivatives, alkali compounds, 2, 13 Indenones, via imine carbonylation, 10, 136 Indenyl-alkoxo complexes, with Ti(IV), 4, 500 Indenyl-amido complexes, with Ti(IV), 4, 454 Indenyl-amido dimethyl complexes, with Ti(IV), 4, 442 Indenyl bridges, in [Pg.126]

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