New mixed tetranuclear metal carbonyls of group VIIIB

Martinengo, Secondo; Chini, P.; Albano, Vincenzo G.; Cariati, F.; Salvatori, T.

doi:10.1016/s0022-328x(00)95055-1

Cited by 119 publications

(21 citation statements)

References 20 publications

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“…Previously, we developed Co/Rh heterobimetallic nanoparticles as a catalyst for the Pauson‐Khand reaction (PKR) . Co 2 Rh 2 nanoparticles [derived from Co 2 Rh 2 (CO) 12 ] were immobilized on charcoal (Co 2 Rh 2 /C). Black Co 2 Rh 2 /C is ferromagnetic and insoluble in a reaction medium and thus, it can be easily separated from the reaction mixture.…”

Section: Methodsmentioning

confidence: 99%

“…Moreover, this compound exhibited high catalytic activity in the PKR as well as in many other useful reactions, such as carbonylation, aminocarbonylation,, and hydroformylation . In a more recent study, we revealed the usefulness of these reactions in the hydrogenation of nitroarene, reductive amination of aldehydes and ketones with amines in the presence of carbon monoxide, reductive cyclization of 2‐(2‐nitroaryl)‐acetonitriles to indoles, and the reductive amination of aldehydes with nitroarenes . From our previous studies, we conjectured that deamination from a suitable substrate was a feasible process in the presence of Co 2 Rh 2 /C.…”

Section: Methodsmentioning

confidence: 99%

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Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co‐Rh Heterobimetallic Nanocatalyst

et al. 2018

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Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co 2 Rh 2 /C as catalyst (molar ratio Co:Rh = 2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co 2 Rh 2 /C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co‐Rh Heterobimetallic Nanocatalyst

et al. 2018

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“…4316 furnished with a magnetic stirrer. Most of the starting materials and reference compounds were purchased from Aldrich Chemical Co. Rh 2 Co 2 (CO) 12 (3) [16], Ru 3 (CO) 9 (PPh 3 ) 3 (4) [17] and the various polycyclic di-and tetrahydroarenes [4] were prepared as described in the literature.…”

Section: Generalmentioning

confidence: 99%

Activation of Metal-Carbonyl Clusters by their Encapsulation Within Alumina Sol-Gel Matrices

Eliau

Avnir

Eisen

et al. 2005

J Sol-Gel Sci Technol

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Abstract. Entrapment of Ru 3 (CO) 12 and Os 3 (CO) 12 within alumina sol-gel matrices, (obtained by hydrolysis and polycondensation of a THF solution of aluminum isopropoxide) converts these clusters into highly active, leachproof and recyclable hydrogen transfer catalysts. Likewise Rh 2 Co 2 (CO) 12 which, in its silica sol-gel entrapped form, neither promotes the isomerization of allylbenzene nor the disproportionation of dihydroarenes, becomes upon its entrapment in an alumina sol-gel matrix, an efficient and recyclable catalyst for these reactions. While the entrapped osmium cluster promotes at 100-110• C and 20 bar only the hydrogenation of alkenes, the ruthenium analog catalyzes also the saturation of the aromatic C C bonds. The hydrogenations take place via the hydride mechanism. XPS and TEM studies revealed that the carbonyl clusters do not decompose to give detectable amounts of (entrapped) metal particles during the encapsulation as well as during the catalytic processes.

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“…[17] A solution containing the heterobimetallic carbonyl compound was injected into a solution of o-dichlorobenzene, oleic acid, and trioctylphosphine oxide at 180 8C. Heating the resulting solution at 180 8C for 2 h afforded a black solution.…”

Section: Synthesis and Characterization Of Co/rh Heterobimetallic Nanmentioning

confidence: 99%

Immobilized Co/Rh Heterobimetallic Nanoparticle‐Catalyzed Pauson–Khand‐Type Reaction

Park

Chung

2005

Adv Synth Catal

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Co/Rh heterobimetallic nanoparticles were prepared from cobalt-rhodium carbonyl clusters [Co 2 Rh 2 (CO) 12 and Co 3 Rh(CO) 12 ] and immobilized on charcoal. HR-TEM revealed that the size of the heterobimetallic nanoparticles was ca. 2 nm and ICP-AES analysis showed a 2 : 2 and a 3 : 1 cobalt-rhodium stoichiometry (Co 2 Rh 2 and Co 3 Rh 1 ) in the heterobimetallic nanoparticles. The Co/Rh heterobimetallic nanoparticles immobilized on charcoal were used as a catalyst in the Pauson-Khand-type reaction under 1 atm of CO. The catalytic reactivity was highly dependent upon the ratio of Co : Rh with the highest reactivity being observed when the ratio was 2 : 2 (Co 2 Rh 2 ). The Co 2 Rh 2 immobilized catalyst is quite an effective catalyst for intra-and intermolecular Pauson-Khand-type reactions. When the immobilized Co 2 Rh 2 catalyst was used as a catalyst in the PausonKhand-type reaction in the presence of an aldehyde instead of carbon monoxide, the catalytic system was highly efficient. When the reaction was carried out in the presence of chiral diphosphines, ee values up to 87% were observed. The catalytic system can be reused at least five times in the presence of chiral diphosphines without loss of catalytic activity and enantioselectivity. The addition of Hg(0), a known heterogeneous catalyst poison, completely inhibits further catalysis. Thus, an environmentally friendly and sustainable process was developed.

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New mixed tetranuclear metal carbonyls of group VIIIB

Cited by 119 publications

References 20 publications

Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co‐Rh Heterobimetallic Nanocatalyst

Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co‐Rh Heterobimetallic Nanocatalyst

Activation of Metal-Carbonyl Clusters by their Encapsulation Within Alumina Sol-Gel Matrices

Immobilized Co/Rh Heterobimetallic Nanoparticle‐Catalyzed Pauson–Khand‐Type Reaction

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