Dinuclear Ru/Os Compounds with Metal–Metal Bonds

Wilton‐Ely, James D. E. T.

doi:10.1016/b0-08-045047-4/00184-9

Cited by 4 publications

(4 citation statements)

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“…Transition-metal clusters often exhibit unique reactivity, the so-called “multimetallic activation”, stemming from multiple coordination of substrates . We have synthesized dinuclear to pentanuclear transition-metal polyhydrido clusters supported by substituted cyclopentadienyl groups, which undergo smooth cleavage of thermodynamically robust bonds such as C–H bonds in alkanes and N–H bonds in ammonia …”

mentioning

confidence: 99%

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η⁵-C₅Me₅): Enhancement of Reactivity toward CO₂by Introduction of the Cn* Ligand

2012

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The novel mixed-ligand diruthenium trihydrido complex Cn*Ru(μ-H)3RuCp* (2; Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane, Cp* = η5-C5Me5) was synthesized, and its structure was determined by an X-ray diffraction study. Density functional theory (DFT) calculations for 2 revealed that the electron density at the Cn*-ligated ruthenium atom is higher than that at the Cp*-ligated ruthenium atom. Whereas the unmixed Cp*,Cp*-ligated Cp*Ru(μ-H)4RuCp* (5) exhibited no reactivity toward CO2 at 20 atm, the mixed-ligand complex 2 reacted with CO2 smoothly at atmospheric pressure and afforded the bis(μ-formato) complex Cn*Ru(μ-η1:η1-O2CH)2(μ-H)RuCp* (4) quantitatively.

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mentioning

confidence: 99%

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η⁵-C₅Me₅): Enhancement of Reactivity toward CO₂by Introduction of the Cn* Ligand

2012

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“…Multimetallic complexes are known to undergo oxidative addition by reduction of the formal metal-metal bond, that is, the electrons involved in metal-metal bonding formally compensate the formation of new metal-ligand bonds. [52][53][54][55] The characteristics of multimetallic systems may allow "multielectron transfer" biomimetic chemistry, which is key to the transformation of small molecules such as N 2 and CO 2 . [56][57][58] Peters et al already demonstrated a proof-of-principle, and a new strategy using borane ligands would expand the chemistry to include small-molecule activation.…”

Section: Similarity Of Reactivity Observed In Metalloboratranes and Imentioning

confidence: 99%

Recent Developments in the Coordination Chemistry of Multidentate Ligands Featuring a Boron Moiety

Kameo

Nakazawa

2013

Chemistry An Asian Journal

135

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Synergistic effects between a transition metal and an appropriate ligand are required to promote a desired catalytic reaction. Ancillary ligands, provided by the versatile functionality of certain elements, give rise to an almost infinite potential for catalytic applications. Recently, the study of the synergistic effect between transition metals and boron has become easy on account of the development of various rigid multidentate frameworks. In this Review, we mainly focus on the chemistry of σ-acceptor (Z-type) borane ligands, particularly the key achievements of their unique reactivity and catalytic applications. Conceptually, the unique character of σ-acceptor borane ligands provides a new strategy for developing remarkable reactivity and novel catalytic applications. This study discusses recent developments in the field in this context. The chemistry of boron-based multidentate ligands that involve a covalent M-B bond such as the boryl ligand (-BR2), in which a boron moiety serves as a strong electron-donating ligand, is also rapidly developing. The effect of the boryl ligand on a metal center is totally different from that of the borane (-BR3) ligand, and different boron-based functionalities confer opposing electronic properties to the metal center. The interesting character of boryl-based chelating ligands augments their unique coordination chemistry, which is also summarized in this context.

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“…Transition-metal cluster complexes often exhibit specific reactivity based on the cooperative behavior of adjacent metallic centers. The so-called cluster effect mainly stems from the interaction between substrates and multiple metallic centers, which function as binding and activation sites and significantly accelerate the reaction that involves less reactive molecules . We have thus far synthesized di- to pentanuclear transition-metal polyhydrido clusters supported by substituted cyclopentadienyl groups and reported on the so-called multimetallic activation of robust bonds such as the C–H and C–C bonds in alkanes and N–H bonds in ammonia, under thermal conditions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of Mixed-Ligand Dinuclear Ruthenium Polyhydrido Complexes Supported by 1,4,7-Trimethyl-1,4,7-triazacyclononane and Bulky Phosphine Ligands

Namura

Suzuki

2014

Organometallics

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To construct electronically and sterically anisotropic reaction sites of dinuclear cluster, mixed-ligand diruthenium pentahydrido complexes [Cn*Ru(μ-H) 3 Ru-(H) 2 (PR 3 ) 2 ] + (Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane; R = Cy (3a), i Pr (3b), cyclopentyl (Cyp, 3c)) were synthesized by the reaction of [Cn*RuH(H 2 ) 2 ] + (1) with Ru-(H) 2 (H 2 ) 2 (PR 3 ) 2 (R = Cy (2a) i Pr (2b), Cyp (2c)). The treatment of 3a−c with KH afforded the corresponding neutral tetrahydrido complexes Cn*Ru(μ-H) 3 RuH(PR 3 ) 2 (R = Cy (4a), i Pr (4b), Cyp (4c)). The structures of 3 and 4 were confirmed by X-ray diffraction studies. Introduction of the Cn* ligand into the cluster increased the electron density at the Cn*ligated metal center and significantly stimulated reactivitiy toward molecular nitrogen and carbon dioxide. Complexes 3a−c reacted with molecular nitrogen to produce the terminal dinitrogen complexes [Cn*Ru(N 2 )(μ-H) 2 RuH(PR 3 ) 2 ] + (R = Cy (5a), i Pr (5b), Cyp (5c)), which readily underwent dimerization to form the bridging dinitrogen complexes [(μ-N 2 ){RuCn*(μ-H) 2 RuH(PR 3 ) 2 } 2 ] 2+ (R = i Pr (6b), Cyp (6c)), through the liberation of N 2 . Cationic complexes 3a−c reacted with CO 2 to produce the bridging formato complexes [Cn*Ru(μη 1 :η 1 -O 2 CH)(μ-H) 2 Ru(H 2 )(PR 3 ) 2 ] + (R = Cy (7a), i Pr (7b), Cyp (7c)), whereas neutral 4a−c reacted with CO 2 to form the carbonyl complexes [Cn*Ru(CO)(μ-H) 2 RuH(PR 3 ) 2 ] + (R = Cy (9a), i Pr (9b), Cyp (9c)), via cleavage of the CO bond.

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Dinuclear Ru/Os Compounds with Metal–Metal Bonds

Cited by 4 publications

References 382 publications

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η⁵-C₅Me₅): Enhancement of Reactivity toward CO₂by Introduction of the Cn* Ligand

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η⁵-C₅Me₅): Enhancement of Reactivity toward CO₂by Introduction of the Cn* Ligand

Recent Developments in the Coordination Chemistry of Multidentate Ligands Featuring a Boron Moiety

Synthesis, Structure, and Reactivity of Mixed-Ligand Dinuclear Ruthenium Polyhydrido Complexes Supported by 1,4,7-Trimethyl-1,4,7-triazacyclononane and Bulky Phosphine Ligands

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Dinuclear Ru/Os Compounds with Metal–Metal Bonds

Cited by 4 publications

References 382 publications

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η5-C5Me5): Enhancement of Reactivity toward CO2by Introduction of the Cn* Ligand

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η5-C5Me5): Enhancement of Reactivity toward CO2by Introduction of the Cn* Ligand

Recent Developments in the Coordination Chemistry of Multidentate Ligands Featuring a Boron Moiety

Synthesis, Structure, and Reactivity of Mixed-Ligand Dinuclear Ruthenium Polyhydrido Complexes Supported by 1,4,7-Trimethyl-1,4,7-triazacyclononane and Bulky Phosphine Ligands

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Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η⁵-C₅Me₅): Enhancement of Reactivity toward CO₂by Introduction of the Cn* Ligand

Synthesis and Structure of a Mixed-Ligand Dinuclear Ruthenium Trihydrido Complex Supported by Cn* and Cp* Ligands (Cn* = 1,4,7-Trimethyl-1,4,7-triazacyclononane, Cp* = η⁵-C₅Me₅): Enhancement of Reactivity toward CO₂by Introduction of the Cn* Ligand