Preparations and Characterization of Some Carbonyl(1-cyanoethyl)ruthenium(II) Complexes

Hiraki, Kei; Ochi, Naoyuki; Kitamura, Tsuneyuki; Sasada, Yoko; Shinoda, Sumió

doi:10.1246/bcsj.55.2356

Cited by 25 publications

(2 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5 The cyanoethyl complex [TpRu-{CH(CN)CH 3 }(CO)(PPh 3 )] was prepared from the chlorobridged dimer [Ru 2 (µ-Cl) 2 {CH(CN)CH 3 } 2 (CO) 2 (PPh 3 ) 4 ]. 6 It is worth pointing out that the carbonyl hydride complex 1a has been prepared previously by treatment of RuHCl(CO)(PPh 3 ) 3 with sodium hydrotris(pyrazolyl)borate in refluxing toluene. 7 All the (σ-organyl)[hydrotris(pyrazolyl)borato]ruthenium complexes reported to date have been prepared by reacting KTp or NaTp with ruthenium complex precursors containing the σ-organyl groups.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

et al. 1997

View full text Add to dashboard Cite

Treatment of TpRuCl(PPh 3 )(CH 3 CN) (Tp ) hydrotris(pyrazolyl)borate) with NaBH 4 in ethanol did not yield the expected hydride complex TpRuH(PPh 3 )(CH 3 CN) (2) but rather the methyl carbonyl complex TpRu(CH 3 )(CO)(PPh 3 ) (1b). Formation of 1b was due to decarbonylation of ethanol by 2 generated in situ by NaBH 4 reduction of TpRuCl(PPh 3 )(CH 3 -CN). Analogous reactions in the presence of other primary alcohols RCH 2 OH (R ) H, C 2 H 5 , n-C 3 H 7 , C 6 H 5 , C 6 H 4 CH 3 -4, and C 6 H 4 Cl-4) led to the corresponding σ-organyl complexes TpRuR(CO)(PPh 3 ). A common feature of the reactions is that the R groups of alcohols RCH 2 -OH become the σ-organyl groups in the final metal complexes. A mechanism involving metal-η 2 -aldehyde and -η 2 -dihydrogen intermediates is proposed for the decarbonylation reaction. This is supported by the observation of the η 2 -dihydrogen complex TpRuH(H 2 )-(PPh 3 ) (3) during the decarbonylation reaction. 3 was synthesized independently by heating a THF solution of 2 under 40 atm of H 2 at 60 °C for 48 h or by heating 2 in CH 3 OH at 60 °C under 6 atm of H 2 for 5-6 h.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

et al. 1997

View full text Add to dashboard Cite

show abstract

“…,O]carbonyl(triphenylphosphine)ruthenium(~~)) (5).-A toluene suspension (20 cm3) containing complex (3) (0.14 g, 0.16 mmol) was refluxed for 5 h. After the solvent was evaporated under reduced pressure, the residue was recrystallized from 3.96 (A' + A", q, 2 H, OCH,) 4.01 (B'q, 1.1 H, OCH,) 4.09 (A"q, 0.9 H, OCH,) 4.10 (B"q, 0.9 H, OCH,) 4.40 (B"q, 0.9 H, OCH,)…”

Section: Preparationofdi-p-chloro-bis( [ 12-(bi~-ethoxycarbonyl)ethyl-c'mentioning

confidence: 99%

Synthesis of some [1,2-bis(alkoxycarbonyl)ethyl]ruthenium(II) complexes and their catalytic activities for cis-trans isomerization of dialkyl maleates

Hiraki¹,

Ochi²,

Takaya³

et al. 1990

J. Chem. Soc., Dalton Trans.

Self Cite

View full text Add to dashboard Cite

The hydridoruthenium(1i) complex [RuCI(CO)H( PPh,),](1) reacted smoothly with dimethyl maleate and diethyl maleate at room temperature to give insertion products,(2; R = Me) and (3; R = Et), respectively. Complex (2) was also formed by reaction of (1 ) with dimethyl fumarate. Complexes (2) and (3) were converted into binuclear complexes [{hu[CH(CO,R)CH,C(b)OR](p-CI)(CO)(PPh,)},] (4; R = Me) and (5; R = Et), respectively, by heating above 100 "C. Complex (4) reacted with Na[BH(pz),] (pz = 1 -pyrazolyl) at ambient temperature to afford [Ru{CH(CO,Me)CH,CO,Me}(CO){BH(pz),)( PPh,)]. Complexes (I), (2), and ( 4) were found to catalyze cis-trans isomerization of dialkyl maleates above 100 "C. A kinetic study of the isomerization of dimethyl maleate revealed that the reaction rates were proportional to the concentrations of both the substrate and the catalyst, and that the ratio of the catalytic constants per ruthenium atom is about 1.6 : 1 .O: 0.36 for (1 ), (2), and (4), respectively, at 120 "C. Addition of PPh, to the catalyst accelerated the reaction rates. It is deduced that the

show abstract

η ¹ σ‐Alkyl Complexes by Addition of Metal Hydrides to Monoolefins

Bergbreiter¹

1991

Inorganic Reactions and Methods

View full text Add to dashboard Cite

Preparations and Characterization of Some Carbonyl(1-cyanoethyl)ruthenium(II) Complexes

Cited by 25 publications

References 11 publications

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of some [1,2-bis(alkoxycarbonyl)ethyl]ruthenium(II) complexes and their catalytic activities for cis-trans isomerization of dialkyl maleates

η ¹ σ‐Alkyl Complexes by Addition of Metal Hydrides to Monoolefins

Contact Info

Product

Resources

About

Preparations and Characterization of Some Carbonyl(1-cyanoethyl)ruthenium(II) Complexes

Cited by 25 publications

References 11 publications

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H2)(PPh3) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H2)(PPh3) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of some [1,2-bis(alkoxycarbonyl)ethyl]ruthenium(II) complexes and their catalytic activities for cis-trans isomerization of dialkyl maleates

η 1 σ‐Alkyl Complexes by Addition of Metal Hydrides to Monoolefins

Contact Info

Product

Resources

About

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

η ¹ σ‐Alkyl Complexes by Addition of Metal Hydrides to Monoolefins