Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems

Bruce, Michael I.; Buntine, Mark A.; Costuas, Karine; Ellis, Brian; Halet, Jean‐François; Low, Paul J.; Skelton, Brian W.; White, Allan H.

doi:10.1016/j.jorganchem.2004.07.030

Cited by 12 publications

(4 citation statements)

References 59 publications

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“…We have recently undertaken an investigation of the coordination and organometallic chemistry of a number of unusual cyanocarbons [18], and have described the synthesis of complexes [Ru(N"CC"CPh)(PPh 3 ) 2 Cp][PF 6 ] and Ru(C"CC"N)(PPh 3 ) 2 Cp, featuring the cyanoacetylene and cyanoacetylide ligands, respectively [19]. While the phenylpropionitrile ligand is readily displaced by other donor ligands including NCMe and tetracyanoethene (TCNE), the cyanoacetylide complex is a much stronger r-donor, and can be used in the formation of robust homo and hetero-bimetallic compounds such as [{Ru(PPh 3 ) 2 -Cp} 2 (l-C"CC"N)][PF 6 ] and [{Cp(PPh 3 ) 2 Ru}(l-C" CC"N){Fe(dppe)Cp}][PF 6 ].…”

Section: Introductionmentioning

confidence: 99%

Syntheses and molecular structures of group 8 benzonitrile complexes

Cordiner

Albesa‐Jové

Roberts

et al. 2005

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Syntheses and molecular structures of group 8 benzonitrile complexes

Cordiner

Albesa‐Jové

Roberts

et al. 2005

Journal of Organometallic Chemistry

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“…The reactiono f1a with the bromido analogue [RuBr 2 (PPh 3 ) 3 ]s imilarly afforded complex 3a as ab rown precipitate. [16,17] Compared with the bent structure of ketimido complexes of second-row late transition metalss uch as Rh and Pd, [8a, 12h] the obvious structurald ifference of the Ru ketimido complexes is of interest. [7c] The RuÀNb ond is much shorter than those in second-row late transition metal ketimido complexes (RhÀN2 .039, PdÀN1 .999 ), [8a, 12h] which implies stronger interaction between the nitrogen atom and the Ru center.…”

Section: Isolation Of Ru Ketimido Complexesmentioning

confidence: 99%

Generation of Stable Ruthenium(IV) Ketimido Complexes by Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru−N Bond

Shimbayashi

Okamoto

Ohe

2017

Chemistry A European J

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The reaction of an oxime ester with [Ru(PPh ) X ] proceeded smoothly at room temperature to afford a stable Ru ketimido complex as oxidative adduct. The structure of the complex was unambiguously determined by X-ray crystallographic analysis, which showed an almost linear Ru-N-C array. The electronic properties of the nitrogen atom were estimated by DFT calculations, and the results suggested double-bond character of the Ru-N bond. Kinetic studies and consideration of the substituent effect on the oxime ester led to the proposal of a reaction mechanism involving oxidative addition, which could proceed by N,O-chelating coordination to the Ru center prior to N-O bond cleavage. The obtained Ru ketimido complex could be transformed into a ruthenacycle by C-H activation by a concerted metalation-deprotonation mechanism in dichloromethane/methanol. Ru ketimido complexes with a tethered alkyne or alkene moiety underwent chloroamination of unsaturated C-C bonds followed by C-H activation, which resulted in the formation of a ruthenacycle. Considering the LUMO of an isolated Ru ketimido complex, the chloroamination should proceed by a synchronous 1,3-dipolar cycloaddition-type mechanism. Insight into the character and reactivity of Ru ketimido complexes will be helpful for developments in the catalytic transformation of oxime esters.

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“…The IR spectra of compounds 1-4 clearly exhibit the usual n CN vibration bands typical of the cyano groups in the 2100-2300 cm À1 range; significant increases in the wavenumbers with respect to the anion (2239 and 2215 cm À1 for 1, 2201 cm À1 for Et 4 N(C 8 N 5 )) indicate coordination of the polynitrile unit to the metal centre. 28 The IR spectra of hydrated complexes 1-2 also exhibit absorption bands arising from the presence of water (at ca. 3400 and 1640 cm À1 , respectively for n OH and d HOH ).…”

Section: Reactions Of the Tetraethylammonium Salt Of The Pentacyanopr...mentioning

confidence: 99%

Syntheses, structural characterisation and magnetic properties of Fe(ii) and Mn(ii) compounds with the pentacyanopropenido ligand; structural characterisation of a substituted pyrazolo[1,5-a]pyrimidine

et al. 2006

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International audienceReactions between the metal(II) salts [M(CH3CN)n](BF4)2 (M = Fe, n = 6; M = Mn, n = 4) and some organic anionic polynitriles were studied. With the pentacyanopropenide anion pcp− [pcp− = (NC)2CC(CN)C(CN)2−], were obtained, according to the experimental conditions, the new complexes [M(pcp)2(H2O)4] (1, M = Fe; 2, M = Mn) and [M(pcp)2] (3, M = Fe; 4 = Mn). Use of the hexacyano-3,4-diazahexadienediide anion [(NC)2CC(CN)NNC(CN)C(CN)22−] instead of pcp− did not afford polynitrile metal complexes but led to a new organic derivative 5, of formula C10N8H2. Crystallographic studies indicated that the isostructural compounds 1 and 2 involve discrete monomeric units with pcp ligands acting with a monodentate coordination mode and having the metal in a pseudooctahedral trans-MN2O4 environment; however, a rich hydrogen bond system gives rise to a 3D array. Complex 3, which presents metal in a pseudooctahedral MN6 environment, has a 3D structure arising from pcp ligands having an unprecedented μ3-coordination mode. Compound 5 is a bicyclic derivative with a pyrazolo[1,5-a]pyrimidine skeleton. In all derivatives, the organic part is essentially planar and involves a strongly delocalized π system. The magnetic properties of the inorganic complexes have been studied in the 2–300 K range. Fit of the magnetic data indicates high spin complexes with weak antiferromagnetic interactions in 2, 3 and 4 and the presence of a significant zero field splitting of the Fe(II) ion in 1

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Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems

Cited by 12 publications

References 59 publications

Syntheses and molecular structures of group 8 benzonitrile complexes

Syntheses and molecular structures of group 8 benzonitrile complexes

Generation of Stable Ruthenium(IV) Ketimido Complexes by Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru−N Bond

Syntheses, structural characterisation and magnetic properties of Fe(ii) and Mn(ii) compounds with the pentacyanopropenido ligand; structural characterisation of a substituted pyrazolo[1,5-a]pyrimidine

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