Carbon-hydrogen bond activation by transition metal complexes. Oxidative addition of alkyl methacrylate to ruthenium. The structure of hydrido(2-n-butoxycarbonylpropenyl-C1,O)tris(triphenylphosphine)ruthenium(II)

Komiya, Sanshiro; Ito, Takashi; Cowie, Martin; Yamamoto, Akio; Ibers, James A.

doi:10.1021/ja00429a024

Cited by 100 publications

(49 citation statements)

References 18 publications

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“…-The 'H n.m.r. spectrum of (6) showed two triplets at 6 7) and (8) can also be ascribed analogous structures to that of (6), on the basis of their 'H n.m.r. spectra.…”

Section: (S)mentioning

confidence: 65%

Organoruthenium(II) complexes formed by insertion reactions of some vinyl compounds and conjugated dienes into a hydrido–ruthenium bond

Hiraki¹,

Ochi²,

Sasada³

et al. 1985

J. Chem. Soc., Dalton Trans.

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yo -machi, Nagasaki 852, Japan The hydridoruthenium(1i) complex [RuCI(CO)H (PPh,),] (1 ) reacted easily with methyl acrylate and N,N-dimethylacrylamide to give the corresponding insertion products, [Ru{CH,CH,C(O) -OMe}CI(CO)(PPh,),] * It was erroneous that in ref. 26, (8) was ascribed to a structure in which the two PPh, ligands were located at trans positions to each other. The 'H n.m.r. data of (8) in ref. 26 are revised in Table 2, owing to the correction of calibration.

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“…-The 'H n.m.r. spectrum of (6) showed two triplets at 6 7) and (8) can also be ascribed analogous structures to that of (6), on the basis of their 'H n.m.r. spectra.…”

Section: (S)mentioning

confidence: 65%

Organoruthenium(II) complexes formed by insertion reactions of some vinyl compounds and conjugated dienes into a hydrido–ruthenium bond

Hiraki¹,

Ochi²,

Sasada³

et al. 1985

J. Chem. Soc., Dalton Trans.

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“…The Ru(1)ÀC(3) and Ru(1)ÀO (1) 4 ], in which RuÀO is a coordinate bond. [20] According to this report, the RuÀC and RuÀO distances are 2.061(10) and 2.246(7) , respectively. The similar length of the RuÀC bond and significantly shorter RuÀO bond in 1 a reflect covalent bonding characters for both.…”

Section: Cationic Carboxylato Complexesmentioning

confidence: 92%

Stoichiometric CH Bond Cleavage Reaction in a Bis(carboxylato)ruthenium(II) Complex and Its Application to the Catalytic H–D Exchange Reaction of Carboxylic Acids

Hirano¹,

Fujimoto²,

Hatagami³

et al. 2013

ChemCatChem

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A cationic complex [Ru{OC(O)CMeCH2‐κ2O,O′}(PMe3)4]+CH2CMeCO2− (5 a) and its related carboxylato complexes are newly prepared by the reaction of [cis‐RuH2(PMe3)4] (4) with carboxylic acids in methanol in 76–100 % yield. Complex 5 a reversibly transforms to the neutral form [cis‐Ru{OC(O)CMeCH2‐κ1O}2(PMe3)4] (2 a) in nonpolar solvents. Complex 2 a reversibly liberates a PMe3 group to give [Ru{OC(O)CMeCH2‐κ1O}{OC(O)CMeCH2‐κ2O,O′}(PMe3)3] (12 a) from which a stereoselective CH bond cleavage reaction occurs to give a ruthenalactone [Ru{OC(O)CMeCH‐κ2O,C}(PMe3)4] (1 a) from the release of methacrylic acid. Complexes 2 a and 5 a also give 1 a but the prior dissociation of a PMe3 is indispensable for the CH bond cleavage reaction. Complex 1 a establishes an equilibrium with 2 a (or 5 a) in solution. In this reaction, one coordinated carboxylato ligand is engaged in the CH bond cleavage reaction as a proton acceptor, but neither the added carboxylato anion nor typical proton acceptors such as proton sponge assist the reaction. In [D4]MeOH, a catalytic stereospecific deuteration of carboxylic acids has been achieved by 4, in which the equilibrium between 5 a and 1 a plays a key role.

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“…The carbonyl functional groups are extended across the Ru(1)-Ru(2) bond and coordinated to the adjacent Ru(1) atom with distances Ru(1)-O( 14)=2.145(3) A and Ru(1)-O( 16)=2.117(3) A. These values are typical for the O --+ Ru dative bond in triruthenium complexes containing such r/2-carbonyl group [11], but are slightly shorter than that observed in dinuclear (CsMes)zRu2(kt-H)[C2Hz(CO2Me)2 ] [C2H(CO2Me):] (2.23(1) A) [ 12] and mononuclear (Ph3P)3RuH[CH = CMe(CO2Bu)] (2.246(7)A) [13], in which the carbonyl oxygen is also coordinated to ruthenium atom. Therefore, the structure of 1 represents the first example in which the dimethyl maleate ligand serves as a six-electron donor through the coordination of its carbon--carbon double bond and both carbonyl fragments.…”

Section: Resultsmentioning

confidence: 99%

New electron-deficient alkene and alkyne derivatives of Ru5(μ5-C)(CO)15: The syntheses and crystal structure analyses of Ru5(μ5-C)(CO)13 [C2H2(CO2Me)2] and Ru5(μ5-C)(CO)15 [C2(CO2Me)2]

et al. 1997

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Treatment of carbido cluster Rus(/zs-C)(CO)~5 with Me3NO in acetonitrile solution followed by addition of dimethyl maleate or dimethyl acetylene dicarboxylate affords new clusters Rus(/zs-C)(CO)~3[C2H2(CO2Me)2] (1) and Rus(/zs-C)(CO)Is[C2(CO2Me)2] (2), respectively. Single crystal X-ray structural studies reveal that both complexes contain a wingtip-bridged butterfly pentametallic skeleton. In complex 1 the maleate fragment is coordinated to one wingtip Ru atom through its carbon-carbon double bond and to the adjacent Ru atom by the formation of two O ~ Ru dative bonding interactions, while the acetylene dicarboxylate fragment in 2 is best considered as a cis-dimetaUated alkene, linking one hinge Ru atom and the nearby Ru atom at the bridged position.

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Carbon-hydrogen bond activation by transition metal complexes. Oxidative addition of alkyl methacrylate to ruthenium. The structure of hydrido(2-n-butoxycarbonylpropenyl-C1,O)tris(triphenylphosphine)ruthenium(II)

Cited by 100 publications

References 18 publications

Organoruthenium(II) complexes formed by insertion reactions of some vinyl compounds and conjugated dienes into a hydrido–ruthenium bond

Organoruthenium(II) complexes formed by insertion reactions of some vinyl compounds and conjugated dienes into a hydrido–ruthenium bond

Stoichiometric CH Bond Cleavage Reaction in a Bis(carboxylato)ruthenium(II) Complex and Its Application to the Catalytic H–D Exchange Reaction of Carboxylic Acids

New electron-deficient alkene and alkyne derivatives of Ru5(μ5-C)(CO)15: The syntheses and crystal structure analyses of Ru5(μ5-C)(CO)13 [C2H2(CO2Me)2] and Ru5(μ5-C)(CO)15 [C2(CO2Me)2]

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