New Ruthenium(IV) Complexes via Oxidative Cp-Ru Bond Rupture and Methyl Activation in Decamethylruthenocene

Deraniyagala, S.P.; Westmoreland, T. David

doi:10.1021/om00003a026

Cited by 9 publications

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“…It is also of interest to note that X-ray crystallographic data indicate that the Cp(centroid)−Ru−Cp(centroid) angle in the [Cp 2 RuBr] + cation is 36.7° . The corresponding angle in [Cp* 2 RuBr] + is 30.7°, and the closest approach of two methyl hydrogen atoms on different Cp* rings is 2.76 Å . The significantly smaller angle in the decamethylruthenocenium is unexpected if intramolecular steric crowding were important.…”

Section: Discussionmentioning

confidence: 99%

Electronic Effects on the Rates of Coupled Two-Electron/Halide Self-Exchange Reactions of Substituted Ruthenocenes

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Westmoreland

2000

Inorg. Chem.

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The complexes (MemCp)(MenCp)Ru (m,n = 1,1; 0.4; 0.5; 1.5) have been synthesized along with the corresponding halometalloceniums [(MemCp)(MenCp)RuX]+ (X = Cl, Br, I). The two-electron/halide transfer self-exchange kinetics have been determined and compared to those of the Cp2Ru/[Cp2RuX]+ parent system. Methylation decreases the rate of exchange monotonically, and plots of ln(kex) vs number of methyl groups are linear for constant X. It is concluded that steric effects do not contribute significantly to the observed kinetics. Thermodynamic studies of halide substitution equilibria support the conclusion that the electronic effects of methylation are essentially additive.

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Section: Discussionmentioning

confidence: 99%

Electronic Effects on the Rates of Coupled Two-Electron/Halide Self-Exchange Reactions of Substituted Ruthenocenes

and

Westmoreland

2000

Inorg. Chem.

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“…Com plex 3 was obtained in 47% yield (0.0784 g, 0.129 mmol). 4 ) was prepared analogously in a yield of 87% (0.0715 g, 0.116 mmol) by the reaction of complex 2 (0.0613 g, 0.134 mmol), Br 2 (0.1006 g, 0.629 mmol), and CH 2 Cl 2 (13 mL) at ~20 °C for 3.5 h. The 1 H and 13 C NMR spectroscopic data are given in Tables 2 and 3 …”

Section: Methodsmentioning

confidence: 99%

“…Earlier, it has been demonstrated 4 that bromine in a heterogeneous toluene-HBr-H 2 4 C 5 Me 4 CH 2 OH]complex. Under these conditions, activation of the C-H bonds in the Me group of the Cp* ring is accompanied by bromination of the Ru atom, functionalization of the CH 2 group, and oxidative cleavage of the Cp*-Ru bonds.…”

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“…Under these conditions, activation of the C-H bonds in the Me group of the Cp* ring is accompanied by bromination of the Ru atom, functionalization of the CH 2 group, and oxidative cleavage of the Cp*-Ru bonds. 4 Cationic complex 1 was synthesized in high yield (87%) by bromination of Cp* 2 Ru in CCl 4 according to a known procedure. 5 The reaction of complex 1 with bro mine was carried out in an NMR tube in CD 2 Cl 2 or in a flask with stirring in CH 2 Cl 2 either at room tem perature or with heating (40 °C).…”

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“…In these reac tion, products derived through Ru-Cp* bond cleavage were not detected. 4 High solubility of reaction products 3-5 in CH 2 Cl 2 and poor solubility in diethyl ether may be indicative of the ionic character of these complexes. Bromination of complex 1 in CH 2 Cl 2 on a preparative scale (see the Experimental section) afforded a mixture of complexes syn 3, syn and anti 4, and syn 5 in a ratio of 59 : 32 : 9.…”

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Functionalization of one or two methyl groups in the [Cp*2RuBr]+Br− complex in the reaction with bromine

et al. 2005

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Ruthenium: Organometallic ChemistryBased in part on the article Ruthenium: Organometallic Chemistry by Ulrich Koelle which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

White

Hanusa

2005

Encyclopedia of Inorganic Chemistry

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In the slightly more than half a century that the organometallic chemistry of ruthenium has had time to develop, it has become clear that the metal's position as the ‘middle child’ of the Group 8 metals is richly reflected in its organometallic derivatives. That is, despite many similarities in the compounds of the iron–ruthenium–osmium triad, addition and elimination reactions of ruthenium, for example, are slower than those of iron but are more facile than those of osmium. Similarly, complexes with hydride and alkyl bonds are generally more stable for ruthenium than for iron, but the ruthenium compounds are often unstable or highly fluxional compared to analogous osmium species. Carbonyl cluster complexes are an important feature of organoruthenium chemistry, and mixed‐ligand carbonyl species with high nuclearity are known, in some cases with more than 10 ruthenium atoms. Interstitial carbides and nitrides are often encountered in ruthenium clusters, and carbonyl hydrides are of interest as hydroformylation catalysts (conversion of alkenes to aldehydes). The cyclopentadienyl ligand is found extensively throughout organoruthenium chemistry, and with a decomposition temperature around 600°C, the sandwich complex ruthenocene Ru(C 5 H 5 ) 2 is among the most stable organometallic compounds known. The stability of ruthenocene and its derivatives allow them to be incorporated as labels into biomolecules such as peptides. Ruthenocene derivatives have also been studied as potential second‐order nonlinear optical materials, and they have played a central role in the development of 30 valence electron triple‐decker cations of the iron group. The high ligand field stabilization of Ru II enables combinations of π‐acceptor ligands together with even the hardest σ‐donors, such as carbonate, sulfate, or nitrate, and hence Ru II carbonyl and phosphine complexes are known with myriad coligand combinations having O, N, or S binding functionalities. In particular, the ability of the (η‐arene)Ru moiety to bind N‐ and O‐ligands has been used to complex various amines, imines, Schiff bases, and amino acids to generate diastereomeric salts, which can serve as chiral catalysts; they are valuable in stereoselective organic syntheses and in the production of biologically active compounds.

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New Ruthenium(IV) Complexes via Oxidative Cp-Ru Bond Rupture and Methyl Activation in Decamethylruthenocene

Cited by 9 publications

References 0 publications

Electronic Effects on the Rates of Coupled Two-Electron/Halide Self-Exchange Reactions of Substituted Ruthenocenes

Electronic Effects on the Rates of Coupled Two-Electron/Halide Self-Exchange Reactions of Substituted Ruthenocenes

Functionalization of one or two methyl groups in the [Cp*2RuBr]+Br− complex in the reaction with bromine

Ruthenium: Organometallic ChemistryBased in part on the article Ruthenium: Organometallic Chemistry by Ulrich Koelle which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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