RuHX(CO)(PR3)2: Can .nu.CO Be a Probe for the Nature of the Ru-X Bond?

Poulton, Jason T.; Sigalas, Michael P.; Folting, Kirsten; Streib, William E.; Eisenstein, Odile; Caulton, Kenneth G.

doi:10.1021/ic00085a043

Cited by 135 publications

(111 citation statements)

References 5 publications

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“…They conclude that −the increase of the ionicity of the RuÀX going up the periodic table dominates over the p-effect and lowers the CO frequency× [29]. They conclude that −the increase of the ionicity of the RuÀX going up the periodic table dominates over the p-effect and lowers the CO frequency× [29].…”

Section: Fig 4 Push-pull Interactionmentioning

confidence: 97%

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Mezzetti

Becker

2002

HCA

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Fluoride has recently found increasing application as coligand both in complexes of late transition metals and as a reagent in asymmetric catalysis. In recent papers, this topic was reviewed, with emphasis on the role played by so-called −push-pull interactions× between the fluoro ligand and a p acid in the stabilization of fluoro complexes with a d 6 or d 8 electron configuration. This picture has led to the concept that fluoride is the strongest p-donor in the halide series. Herein, the latter concept is discussed and criticized. In particular, the effect of the ionicity of the metal-fluoride bond is proposed as an alternative explanation to most of the observations that show a −reversed× halide order. The ionic character of the MÀF bond also accounts for its intrinsic reactivity and suggests some strategies for the stabilizatioin of fluoro complexes, including the use of coordinative unsaturation. The scope and limitations of the application of d 6 and d 8 fluoro complexes in catalysis are also discussed. The most promising application is the use of 16-electron fluoro complexes in the metal-promoted formation of the CÀF bond.

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Section: Fig 4 Push-pull Interactionmentioning

confidence: 97%

Untitled

Mezzetti

Becker

2002

HCA

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“…In this context we note that Caulton and co-workers recently reported that treatment of [Ru-[IrHCl 2 (CO)(PiPr 3 ) 2 ] and [IrHCl 2 (CO)(PPh 3 ){PPh 2 (o-C 6 H 4 OH)}], both containing a planar IrHCl 2 (CO) unit H(OR F )(CO)(PtBu 2 Me) 2 ] (R F ϭ CH 2 CF 3 ) with pyridine also produces a mixture of two isomers of the composition result, the trifluoracetato and iodo derivatives 10 and 11 are less reactive toward PhCHN 2 and upon stirring a solu-[RuH(OR F )(CO)(py)(PtBu 2 Me) 2 ]. [12] tion of the two respective substrates in toluene for 2Ϫ4 h a complex mixture of products is formed. We not only failed to separate the mixture but also found no evidence for the presence of a RuϭCHPh species among the various components.…”

Section: To Givementioning

confidence: 99%

Hydrido(carbonyl) and Hydrido(carbene) Complexes of Ruthenium

Werner¹,

Stüer

Weberndörfer

et al. 1999

Eur. J. Inorg. Chem.

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“…Interestingly, this interaction can be exploited to stabilize operationally unsaturated complexes with a formal 16-electron count [11] [15]. However, five-coordinate fluoro complexes with such an electron configuration are exceedingly rare [11], and most of the reported complexes combining fluoride and phosphine ligands contain strong p-acceptor co-ligands, generally as part of a trans-[FÀMÀCO] fragment featuring push-pull interactions [11] [14] [15]. …”

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confidence: 99%