Monomeric metal hydroxides, alkoxides, and amides of the late transition metals: synthesis, reactions, and thermochemistry

Bryndza, Henry E.; Tam, William

doi:10.1021/cr00089a009

Cited by 620 publications

(416 citation statements)

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“…We have previously reported that TpRu(L)(L′)(NHR) (L ) L′ ) P(OMe) 3 , PMe 3 or L ) CO and L′ ) PPh 3 ) systems react to deprotonate C-H bonds. For example, TpRu(L)(L′)(NHPh) complexes exhibit acid-base equilibria with malononitrile, while TpRu(L)(L′)(NHR) (R ) H or t Bu) complexes form ion pairs due to deprotonation of phenylacetylene.…”

Section: Resultsmentioning

confidence: 99%

“…The solution was filtered through a fine porosity frit, and the volatiles were removed under reduced pressure (0.0771 g, 0.143 mmol, 82%). Orange microcrystalline product was obtained upon recrystallization from pentane at -20°C (isolated yield of the recrystallization is approximately 50% 3 in THF were added. Upon addition of the ammonia solution, a color change from dark orange to yellow was observed.…”

Section: Methodsmentioning

confidence: 99%

“…Experimentally, the addition of ammonia to (PCP)Ru(CO)(Me) (8) forms an equilibrium between (PCP)Ru(CO)(Me)(NH 3 ) and (PCP)Ru(CO)(Me)/NH 3 , and the mixture converts to methane and the cyclometalated complex 7 (Scheme 7). However, whether the formation of 7 and methane is derived from complex 8 or (PCP)-Ru(CO)(Me)(NH 3 ) cannot be definitively determined. Isotopic labeling studies are not useful due to H/D scrambling as described above.…”

Section: Scheme 5 Reaction Of (Pcp)ru(co)(cl) and Meli Yields (Pcp)rmentioning

confidence: 99%

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Synthesis and Reactivity of a Coordinatively Unsaturated Ruthenium(II) Parent Amido Complex: Studies of X−H Activation (X = H or C)

et al. 2004

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Bu 2 ) 2 C 6 H 3 ) has been prepared by two independent routes that involve deprotonation of Ru-(II) ammine complexes. Complex 2 reacts with phenylacetylene to yield the Ru(II) acetylide complex (PCP)Ru(CO)(CtCPh) (5) and ammonia. In addition, complex 2 rapidly activates dihydrogen at room temperature to yield ammonia and the previously reported hydride complex (PCP)Ru(CO)(H). The ability of the amido complex 2 to cleave the H-H bond is attributed to the combination of a vacant coordination site for binding/activation of dihydrogen and a basic amido ligand. Complex 2 also undergoes an intramolecular C-H activation of a methyl group on the PCP ligand to yield ammonia and a cyclometalated complex. The reaction of (PCP)Ru(CO)(Cl) with MeLi allows the isolation of (PCP)Ru(CO)-(Me) (8), and complex 8 undergoes an intramolecular C-H activation analogous to the amido complex 2 to produce methane and the cyclometalated complex. Determination of activation parameters for the intramolecular C-H activation transformations of 2 and 8 reveal identical ∆H q {18(1) kcal/mol} with ∆S q ) -23(4) eu and -18(4) eu, respectively. Density functional theory has been applied to the study of intermolecular activation of methane and dihydrogen by (PCP′)Ru(CO)(NH 2 ) to yield (PCP′)Ru(CO)(NH 3 )(X) (X ) Me or H; PCP′ ) 2,6-(CH 2 -PH 2 ) 2 C 6 H 3 ). The results indicate that the activation of dihydrogen is both exoergic and exothermic. In contrast, the addition of a C-H bond of methane across the Ru-NH 2 bond has been calculated to be endoergic and endothermic. The surprising endoergic nature of the methane C-H activation has been attributed to a large and unfavorable change in Ru-N bond dissociation energy upon conversion from Ru-amido to Ru-ammine.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Scheme 5 Reaction Of (Pcp)ru(co)(cl) and Meli Yields (Pcp)rmentioning

confidence: 99%

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Synthesis and Reactivity of a Coordinatively Unsaturated Ruthenium(II) Parent Amido Complex: Studies of X−H Activation (X = H or C)

et al. 2004

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“…The chemistry of late transition metal-amide complexes (Groups 8-10) has been studied extensively over the past several years (Bryndza & Tam, 1988;Fryzuk & Montgomery, 1989;. In spite of the great interest in these compounds, few have been structurally characterized.…”

Section: Commentmentioning

confidence: 99%

trans-[Ni(Me3Ph)(NHPh)(PMe3)2], a Monomeric NiII–Amide Complex

VanderLende¹,

Boncella²,

Abboud³

1995

Acta Crystallogr C

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“…. H-0 interactions (several alcohol adducts have been reported in palladium alkoxide chemistry [7,9]). However, the stability of 3 and 4 could also arise from the fact that exchange of coordinated methoxide and methanol is much faster than P-hydrogen elimination from the Pd-OMe unit [5].…”

mentioning

confidence: 99%