Some Reactions of Triruthenium Dodecacarbonyl

Johnson, Brian F. G.; Johnston, R. D.; Josty, P. L.; Lewis, Jack; Williams, I. G.

doi:10.1038/213901b0

Cited by 67 publications

(19 citation statements)

References 7 publications

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“…The compound was proved to have a dimeric molecular structure, as shown by the formula [RuBr2(CO)3]2; the calculated composition (Ru 29.3%, Br 46.3%, C 10.4%) is in good agreement with the experimental data of Braca et al (1967). Recently Johnson, Johnston, Josty, Lewis & Williams (1967) have proposed a formula of this type for a product of oxidation of triruthenium dodecacarbonyl with bromine, on the basis of the molecular weight determination.…”

Section: Introductionsupporting

confidence: 73%

Crystal and molecular structure of [RuBr₂(CO)₃]₂

Merlino¹,

Montagnoli²

1968

Acta Crystallogr Sect B

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A three-dimensional structural analysis of a new bromocarbonyl compound of Ru n shows that the compound is to be assigned the formula [RuBr2(CO)3]2. It crystallizes in space group C2/m, with unit-cell dimensions a= 10.74, b=7.44, c=9.42/~, fl= 106°32. Least-squares refinement led to a final agreement factor for the observed reflexions R= 0.103. The molecule possesses molecular point group symmetry 2/m (C2h); the Ru atoms are not bonded to each other directly but by means of two bromine bridges. The observed lengthening of non-bridging metal halide bond has been tentatively interpreted as due to the trans effect of the carbonyl ligand.

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Section: Introductionsupporting

confidence: 73%

Crystal and molecular structure of [RuBr₂(CO)₃]₂

Merlino¹,

Montagnoli²

1968

Acta Crystallogr Sect B

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“…[3,12] Although compounds [Ru 4 (CO) 10 (µ 4 ,η 2 -CϭCHiPr)(OR)(PPh 2 )] (R ϭ H, Et) [7] and [Fe 4 (CO) 12 {µ 4 ,η 2 -CϭC(OMe)R}] (R ϭ OMe, Me) [9a] show a butterfly geometry, a rhombus frame has been observed in the compound [Os 4 (CO) 12 (µ 3 -S){µ 4 ,η 2 -Cϭ C(Ph)H}].…”

Section: Resultsmentioning

confidence: 99%

“…These compounds have been characterised by analytical and spectroscopic data and the structures of some of them have been confirmed by X-ray diffraction. 10 (µ 4 ,η 2 -CϭCHiPr)(OR)(PPh 2 )] (R ϭ H, Et). [7] On the other hand, 1 H NMR resonances at δ ϭ 4.50 [8] and the triosmium cluster [Os 3 (CO) 9 (µ-H)(µ-SPh){µ 3 ,η 2 -(CCH 2 -CH 2 C)}] has been isolated from cyclobutenyl thioether.…”

Section: Introductionmentioning

confidence: 99%

Activation of C−S Bonds in Organosulfur Compounds Containing α,β‐Unsaturated Ketone Systems by Carbonylruthenium and ‐iron Complexes

et al. 2003

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Vinylidenetetraruthenium clusters have been obtained from the reactions between [Ru3(CO)12] and [CH3C(O)CH=C(SCH3)2] or [(C5H5)Fe{C5H4CH=CHC(O)CH=C(SCH2CH2S)}] by cleavage of the S−C sp2 bonds in these ligands. An excess of [CH3C(O)CH=C(SCH3)2] afforded the dinuclear complex [Ru2(CO)4(μ‐SCH3)2{η2:κ‐C,O‐C(SCH3)CHC(O)CH3}2], which was then converted into the vinylidene cluster [Ru4(CO)10(μ‐SCH3)2{μ4,η3:κ‐C,C,O‐C=CHC(O)CH3}] in the presence of more of the carbonylruthenium complex. However, the carbonyliron complex led to the formation of the dinuclear compounds [Fe2(CO)4(μ‐SCH3)2{η2:κ‐C,O‐C(SCH3)CHC(O)CH3}2] and [Fe2(CO)5{μ,η4:κ‐C,O,S,S‐(SCH2CH2S)C=CHC(O)CH=CHC5H4}Fe(C5H5)]. All of the new complexes exhibit a pentametallacycle group as a consequence of the rupture of the S−C bonds, as well as the presence of the C(O)R substituent in these ligands. The compounds have been characterised by analytical and spectroscopic data and the crystal structures of some of them have been solved by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…After the addition of Br 2 , rapid removal of the heating bath is required in order to prevent the reaction of [Os 3 (CO) 12 (Br) 2 ] with additional Br 2 producing at this stage undesired [Os 2 (CO) 8 (Br) 2 ] that is known to transform into [Os 2 (CO) 6 (Br) 2 ] at elevated temperatures. [27] Similar oxidative addition of X 2 (X = Cl, Br, I) to [Ru 3 (CO) 12 ] was reported [28,29] to yield the mononuclear complex cis-[Ru(CO) 4 (X) 2 ] as the initial product, which reflects the increasing stability of the metal-metal bonds towards oxidation on descending the periodic table. Unfortunately, the synthetic strategy depicted in Scheme 1 could therefore not be applied for the synthesis of the isostructural cluster [Ru 2 Os(CO) 12 ].…”

Section: Synthesis Of [Os 2 Ru(co) 12 ] (1)mentioning

confidence: 99%

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]

et al. 2005

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A new synthetic route towards the mixed-metal cluster [Os 2 -Ru(CO) 12 ] is described together with the syntheses of its PPh 3 and iPr-AcPy (iPr-AcPy = 2-acetylpyridine-N-isopropylimine) derivatives. The molecular structures of the novel clusters [Os 2 Ru(CO) 11 (PPh 3 )] and [Os 2 Ru(CO) 10 (iPr-AcPy)] were determined on the basis of crystalline solid solutions of the Os 2 Ru and corresponding Os 3 species. The structures reveal that coordination of the Lewis bases occurs exclusively at the ruthenium site of [Os 2 Ru(CO) 12 ], which is in agreement with density functional theory (DFT) calculations on several structural isomers of these compounds. According to the time-dependent DFT results, the lowest optically accessible excited state of [Os 2 Ru(CO) 10 (iPr-AcPy)] has a prevailing σ(Ru-Os2)-π*(iPr-AcPy) character, with a partial σσ*(Ru-Os2) contribution. In weakly coordinating 2-chlorobutane, the excited state has a lifetime τ = 10.4 ± 1.2 ps and produces biradicals considerably faster than observed for [Os 3 (CO) 10 (iPr-AcPy) (τ = 25.3 ± 0.7 ps). In coordinating acetonitrile, the excited state of [Os 2 Ru(CO) 10 (iPr-AcPy)] decays mono-exponentially with a lifetime τ = 2.1 ± 0.2 ps. In contrast to [Os 3 (CO) 10 (iPr-AcPy)]

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Some Reactions of Triruthenium Dodecacarbonyl

Cited by 67 publications

References 7 publications

Crystal and molecular structure of [RuBr₂(CO)₃]₂

Crystal and molecular structure of [RuBr₂(CO)₃]₂

Activation of C−S Bonds in Organosulfur Compounds Containing α,β‐Unsaturated Ketone Systems by Carbonylruthenium and ‐iron Complexes

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]

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Some Reactions of Triruthenium Dodecacarbonyl

Cited by 67 publications

References 7 publications

Crystal and molecular structure of [RuBr2(CO)3]2

Crystal and molecular structure of [RuBr2(CO)3]2

Activation of C−S Bonds in Organosulfur Compounds Containing α,β‐Unsaturated Ketone Systems by Carbonylruthenium and ‐iron Complexes

Heterosite Effects in Novel Heteronuclear Clusters [Os2Ru(CO)11(PPh3)] and [Os2Ru(CO)10(2‐acetylpyridine‐N‐isopropylimine)]

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Product

Resources

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Crystal and molecular structure of [RuBr₂(CO)₃]₂

Crystal and molecular structure of [RuBr₂(CO)₃]₂

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]