Synthesis and Property of Diruthenium Complexes Containing Bridging Cyclic Diene Ligands and the Reaction of Diruthenium Tetrahydrido Complex with Benzene Forming a μ-η2:η2-Cyclohexadiene Complex via Partial Hydrogenation on a Ru2 Center

Takao, Toshiro; Obayashi, Nozomi; Zhao, Bo; Akiyoshi, Kazunori; Omori, Hideki; Suzuki, Hiroharu

doi:10.1021/om200728e

Cited by 23 publications

(29 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The π-bonded C(2)C(3) distance of 1.420(11) Å is comparable to the inner C(3)–C(3#) distance (1.469(14) Å). This implies that there is a localization of the π electrons at C(2)C(3) bonds, as seen in previous μ-η 2 :η 2 -diene complexes. , …”

Section: Results and Discussionsupporting

confidence: 73%

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

et al. 2017

Self Cite

View full text Add to dashboard Cite

A novel triruthenium hydrido cluster, (Cp*Ru)3(μ3-H)(μ-H)2(μ-CO) (4; Cp* = η5-C5Me5), having a bridging CO ligand was synthesized by the reaction of {Cp*Ru(μ-H)}3(μ3-O) (3) with methanol. Upon introduction of a CO ligand, the cyclic voltammogram of 4 demonstrated a significant shift of the redox potential in the positive direction in comparison to a pentahydrido complex, {Cp*Ru(μ-H)}3(μ3-H)2 (1), which adopts the same 44-electron configuration. Owing to its coordinatively unsaturated nature, 4 readily reacted with butadiene, terminal alkynes, and alkenes similarly to the parent pentahydrido complex 1. However, the reactivity was slightly different from that of 1, and the influence of the CO ligand at the triruthenium site was evaluated by the reaction of various unsaturated hydrocarbons. The reaction of 4 with 1,3-dienes yielded a diene adduct, {Cp*Ru(μ-H)}3(μ-η2:η2-s-cis-H2CCRCHCH2)(CO) (5a, R = H; 5b, R = Me) without elimination of dihydrogen. In the same manner as for 1, 4 reacted with phenylacetylene to yield a μ3-η2:η2(⊥)-alkyne complex, (Cp*Ru)3(μ-H){μ3-η2:η2(⊥)-PhCCH}(μ3-CO) (7a); in contrast, an isomeric μ3-pentenylidene complex, (Cp*Ru)3(μ-H){μ3-η2-CC(nPr)H}(μ-CO) (9b), was obtained by reaction with 1-pentyne. A series of products was obtained by the reaction of 4 with ethylene molecules. A μ3-ethylidyne complex, (Cp*Ru)3(μ-H)2(μ3-CMe)(μ-CO) (11), was initially formed, accompanied by the formation of ethane at ambient temperature. The treatment of 11 with ethylene resulted in the removal of hydrido ligands, affording a μ3-vinylidene complex, (Cp*Ru)3(μ-H)(μ3-η2-CCH2)(μ-CO) (9a). At higher temperatures, a second ethylene molecule was incorporated in the triruthenium plane and an equilibrated mixture of a μ3-ethylidyne−μ-ethylidyne complex, (Cp*Ru)3(μ-H)(μ-CMe)(μ3-CMe)(μ-CO) (13), and μ3-ethylidyne−μ-vinyl complex, (Cp*Ru)3(μ-H)(μ3-CMe)(μ-η2-CHCH2)(μ-CO) (12), was obtained. The formation of a μ3-η3-C3 ring on the Ru3 plane was observed upon the thermolysis of the equilibrated mixture at 180 °C, which clearly demonstrates the coupling of the two C2 moieties placed on each face of the triruthenium plane.

show abstract

Section: Results and Discussionsupporting

confidence: 73%

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…[36][37][38][39] Additionally, the change in angle around the nitrogen in XylNC from linear to bent (126.3 (2) ) conrms reduction of the C-N triple bond. This buttery conguration has been previously observed with transition metal complexes; [40][41][42][43][44][45][46][47] however, they all contain a M-M bond, and those without M-M bonds contain a planar central ring. [48][49][50][51][52] To conrm the nature of the bonding within compound 7 DFT studies were performed again, at the B3LYP-D3/6-311G(d) level of theory.…”

Section: Reactivity Of Dialumenessupporting

confidence: 74%

Dialumenes – arylvs.silyl stabilisation for small molecule activation and catalysis

et al. 2020

View full text Add to dashboard Cite

show abstract

“…As mentioned above, the imidazoline is a 4‐electron donor ligand; therefore, a double bond is required between the two ruthenium atoms according to the effective atomic number (EAN) rule. The distance between the Ru1 and Ru2 center is 2.7435(9) Å, which is similar to that of an isoelectronic dinuclear μ‐η 2 :η 2 ‐cyclohexadiene complex of ruthenium (2.7391(15) Å) 8…”

Section: Methodssupporting

confidence: 54%

Reversible Insertion of 1,3‐Di‐tert‐butylimidazol‐2‐ylidene into a RuH Bond and Bimetallic Activation of a NC Bond of Imidazoline

Kaiho

Suzuki

2011

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

N-Heterocyclic carbenes (NHCs) are strong 2-electron donors and hardly exhibit p-accepting character. [1] NHCs stabilize unsaturated metal centres and have been recently applied as stable spectator ligands in various catalytic transformations of organic molecules in combination with mononuclear transition-metal complexes. [2] However, NHCs can undergo degradation pathways, [3] because they are multifunctional compounds, namely, a lone pair of electrons at C2, which acts as a donor; p-electron lone pairs at N1 and N3; and a C=C double bond between C4 and C5. Because of this multifunctionality, NHCs sometimes undergo a chemical transformation that is possibly related to a deactivation process for catalytically active species.So far, there have been fewer reports on reactions of NHCs with polynuclear complexes than with mononuclear ones, [4] though a variety of patterns are expected to be obtained in the reaction involving a multimetallic system owing to the multifunctional character of NHC molecules. We previously reported the reactions of dinuclear homo-and heterometallic tetrahydrido complexes, [Cp*Ru(m-H) 4 RuCp*] and [Cp*Ru(m-H) 4 OsCp*], with tert-phosphorus ligand that do not contain aryl substituents. [5,6] We examined the reaction of [Cp*Ru(m-H) 4 RuCp*] (1) with 1,3-di-tert-butylimidazol-2-ylidene (ItBu), which is a multifunctional, strong 2-electron donor. We report herein an unprecedented reversible insertion of 1,3-di-tert-butylimidazol-2-ylidene into the ruthenium-hydride bond of 1 and the dynamic process of the resulting dinuclear imidazoline complex. Furthermore, a bimetallic-system-assisted ringopening reaction, that is, the cleavage of the NÀC bond of the imidazoline ligand to generate pseudo-diazaruthenacycle is also reported.The treatment of 1 with 2.3 equivalents of ItBu in tetrahydrofurane at room temperature resulted in the formation of a dinuclear ruthenium m-h 1 :h 2 -4-imidazoline complex 2 as a result of migration of the hydrides from the ruthenium atom to the carbenic carbon (C2) [Eq.(1)]. The yield of the conversion from 1 to 2 reached 56 % under these conditions. The yield inevitably reached a plateau because of the presence of the reverse process, that is, the de-insertion of ItBu. Therefore, a large excess amount of ItBu must be added to carry out the conversion. Time-conversion curves of the reaction of 1 with ItBu are given in the Supporting Information. Complex 2 was efficiently isolated by crystallization from cold pentane (À30 8C).In complex 2, the 4-imidazoline molecule is coordinated as a bridging ligand through a C=C bond and one of the nitrogen atoms. Single crystals of 2 suitable for X-ray diffraction studies were obtained from cold (À30 8C) pentane. The X-ray diffraction data clearly showed the dinuclear structure bridged by 4-imidazoline that was formed by hydride migration to the C2 of the ItBu molecule. The molecular structure of 2 is illustrated in Figure 1 with the relevant bond lengths and angles. [7] The imidazoline molecule is coordinated as 4-electron donor, and...

show abstract

Synthesis and Property of Diruthenium Complexes Containing Bridging Cyclic Diene Ligands and the Reaction of Diruthenium Tetrahydrido Complex with Benzene Forming a μ-η²:η²-Cyclohexadiene Complex via Partial Hydrogenation on a Ru₂ Center

Cited by 23 publications

References 50 publications

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

Synthesis of an Electron-Deficient Triruthenium Hydrido Complex Having a Bridging Carbonyl Ligand: Influence of a CO Ligand on the Properties and Reactivities of a Hydrido Cluster

Dialumenes – arylvs.silyl stabilisation for small molecule activation and catalysis

Reversible Insertion of 1,3‐Di‐tert‐butylimidazol‐2‐ylidene into a RuH Bond and Bimetallic Activation of a NC Bond of Imidazoline

Contact Info

Product

Resources

About