Reductive Cleavage of the N−N Bond of Hydrazine Induced by a Cationic Trinuclear Ruthenium Hexahydride Complex, [(Cp‘Ru)3(μ-H)6]X (Cp‘ = η5-C5Me5; X = 1/2 SO4, BF4, PF6, BPh4) and Dihydrogen

Nakajima, Yumiko; Inagaki, Akiko; Suzuki, Hiroharu

doi:10.1021/om0400494

“…The reaction is reversible, and treatment of 3 with dihydrogen quantitatively affords 1 and ammonia as reported recently 4h. Therefore, the reaction reaches a stationary equilibrium when it is carried out in a closed reaction vessel.…”

supporting

confidence: 60%

“…Complex 1 reacts with ammonia to produce a known μ 3 ‐imido complex, [(Cp*Ru) 3 (μ 3 ‐NH)(μ‐H) 3 ] ( 3 ),4h and dihydrogen as a result of activation of the two NH bonds [Eq. (1)]. …”

mentioning

confidence: 99%

“…As shown in the reaction of hydrazine with triruthenium polyhydrido complexes 1 and [(Cp*Ru) 3 (μ‐H) 6 ]1/2(SO 4 ) ( 5 ), a decrease in the electron density at the ruthenium center accelerates nucleophilic attack of the hydrazine molecule 4g. h On the basis of this observation, we examined the reaction of cationic 5 with ammonia. However, deprotonation to give 1 predominated over nucleophilic attack of ammonia at the metal center because of the protonic character of the hydrido ligand in 5 [Eq.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

Nakajima

¹

,

Kameo

²

,

Suzuki

³

2006

Self Cite

View full text Add to dashboard Cite

NÀH bond activation of amines has attracted increasing attention owing to its applicability to the synthesis of various amino compounds, and the development of a new and effective reaction system for the activation of ammonia must be one of the most important research targets in connection with the transformation of abundant and inexpensive ammonia into a useful amino compound.[1] However, successful examples of activation of the NÀH bond of ammonia are still rare because of both the high NÀH bond dissociation energy ( % 104 AE 2 kcal mol À1 ) [2] and the difficulty in forming an NÀH s complex.[3]The groups of Milstein [1g, i, j] and Hartwig [1k, q] showed independently that some mononuclear iridium(i) complexes exhibited activity towards oxidative addition of ammonia. A highly unsaturated 14 e species with T-shaped geometry was proposed as a reactive intermediate for the NÀH bond cleavage on the basis of kinetic studies.[1q] Some complexes containing a d 0 metal center, such as [Cp* 2 MH 2 ] (M = Zr, Hf; Cp* = pentamethylcyclopentadiene), [1b, c, e] [Cp* 2 ScR], [1f] and [(neopentyl) 3 Ta = C(H)(tBu)], [1h] also activated ammonia to generate amido and nitrido complexes. There have, thus far, been examples of bimetallic oxidative addition to ammonia. A trinuclear carbonyl cluster, [Os 3 (CO) 11 (L)] (L = c-C 6 H 8 or CH 3 CN), effectively activates ammonia with the participation of the two osmium centers to produce the m-amido complex [Os 3 (CO) 10 (m-H)(m-NH 2 )]. [1a, d] A multimetallic system may work more efficiently for bond activation than a monometallic complex owing to the cooperative action of the metal centers. Each metal center would be allotted a part as a binding site and an activation site, and the transition state of the bond-activation step may, therefore, be stabilized.

show abstract

“…This strategy has been employed to synthesise clusters with different auxiliary groups such as ferrocenyl units [3], chiral substituents [4,5], or polymerisable side-chains [6]. Arene ruthenium clusters have an interesting catalytic potential for hydrogenation reactions and other processes [7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and molecular structure of trinuclear mixed-metal cluster cations containing arene and hydrido ligands

Romakh

¹

,

Therrien

²

,

Süß‐Fink

³

2006

Inorganica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Complex 1 reacts with ammonia to produce a known μ 3 ‐imido complex, [(Cp*Ru) 3 (μ 3 ‐NH)(μ‐H) 3 ] ( 3 ),4h and dihydrogen as a result of activation of the two NH bonds [Eq. (1)]. …”

mentioning

confidence: 99%

Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

Nakajima

¹

,

Kameo

²

,

Suzuki

³

2006

Self Cite

View full text Add to dashboard Cite

NÀH bond activation of amines has attracted increasing attention owing to its applicability to the synthesis of various amino compounds, and the development of a new and effective reaction system for the activation of ammonia must be one of the most important research targets in connection with the transformation of abundant and inexpensive ammonia into a useful amino compound.[1] However, successful examples of activation of the NÀH bond of ammonia are still rare because of both the high NÀH bond dissociation energy ( % 104 AE 2 kcal mol À1 ) [2] and the difficulty in forming an NÀH s complex.[3]The groups of Milstein [1g, i, j] and Hartwig [1k, q] showed independently that some mononuclear iridium(i) complexes exhibited activity towards oxidative addition of ammonia. A highly unsaturated 14 e species with T-shaped geometry was proposed as a reactive intermediate for the NÀH bond cleavage on the basis of kinetic studies.[1q] Some complexes containing a d 0 metal center, such as [Cp* 2 MH 2 ] (M = Zr, Hf; Cp* = pentamethylcyclopentadiene), [1b, c, e] [Cp* 2 ScR], [1f] and [(neopentyl) 3 Ta = C(H)(tBu)], [1h] also activated ammonia to generate amido and nitrido complexes. There have, thus far, been examples of bimetallic oxidative addition to ammonia. A trinuclear carbonyl cluster, [Os 3 (CO) 11 (L)] (L = c-C 6 H 8 or CH 3 CN), effectively activates ammonia with the participation of the two osmium centers to produce the m-amido complex [Os 3 (CO) 10 (m-H)(m-NH 2 )]. [1a, d] A multimetallic system may work more efficiently for bond activation than a monometallic complex owing to the cooperative action of the metal centers. Each metal center would be allotted a part as a binding site and an activation site, and the transition state of the bond-activation step may, therefore, be stabilized.

show abstract

Reductive Cleavage of the N−N Bond of Hydrazine Induced by a Cationic Trinuclear Ruthenium Hexahydride Complex, [(Cp‘Ru)₃(μ-H)₆]X (Cp‘ = η⁵-C₅Me₅; X = ¹/₂ SO₄, BF₄, PF₆, BPh₄) and Dihydrogen

Cited by 33 publications

References 22 publications

Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

Synthesis and molecular structure of trinuclear mixed-metal cluster cations containing arene and hydrido ligands

Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

Contact Info

Product

Resources

About