Multimetallic activation of molecular hydrogen, leading to hydrogenation of the coordinated azulenes in di-, tri-, and tetranuclear ruthenium carbonyl complexes

Hideo Nagashima, Akihiro Suzuki, Mitsuharu Nobata, Katsuyuki Aoki, Kenji Itoh

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Abstract

Hydrogenation of di-, tri-, and tetranuclear ruthenium carbonyl complexes bearing guaiazulene or 4,6,8-trimethylazulene as the bridging ligand to bind the multimetallic framework was studied: [μ2 : η-guaiazuIene)Ru2(CO)5 (1a)], [μ2 : η4,6,8-trimethyIazulene)Ru2(CO)5 (1b)], [(/μ3 : η-guaiazuIene)Ru3(CO)7 (2a)], [(μ3 : η-4,6,8-trimethyIazulene)Ru3(CO)7 (2b)], [(μ3 : η-guaiazulene)Ru4(CO)9 (3a)], and [(μ3 : η-4,6,8-trimethylazulene)Ru4(CO)9 (3b)]. Reactions of these di-, tri-, and tetraruthenium complexes with dihydrogen (PH2 = 5-10 atm) at 100 °C resulted in cluster fragmentation and addition of five hydrogen atoms to the azulene ligands to form mononuclear ruthenium carbonyl hydride compounds, [(η5-pentahydroguaiazulenyl)RuH(CO)2 (4a)] or [(η5-pentahydrotrimethylazulenyl)RuH(CO)2 (4b)]. Despite potential formation of several stereoisomers dependent on the addition modes of hydrogen atoms, only one isomer of 4a or 4b was obtained in the hydrogenation. The crystal structure of a derivative of 4a revealed that the addition of hydrogen atoms occurred from the face of the azulene ligand originally bonded with the ruthenium species. Hydrogenation of the di-, tri-, and tetranuclear ruthenium complexes below 100 °C revealed that only the triruthenium compounds reacted with HZ at 50 °C via triruthenium dihydride intermediates: [(μ2 : η-tetrahydroguaiazulene)Ru3H2(CO)7 (6a)] or [(μ2 η-tetrahy-drotrimethylazulene)Ru3H2(CO)7 (6b)]; this indicates that there exists a reaction pathway to achieve facile activation of dihydrogen by the triruthenium clusters.

Original languageEnglish
Pages (from-to)2441-2448
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume71
Issue number10
DOIs
Publication statusPublished - Jan 1 1998

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Azulenes
Ruthenium
Carbon Monoxide
Hydrogenation
Hydrogen
Chemical activation
Ligands
Atoms
Bearings (structural)
Stereoisomerism
Hydrides
Isomers

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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Multimetallic activation of molecular hydrogen, leading to hydrogenation of the coordinated azulenes in di-, tri-, and tetranuclear ruthenium carbonyl complexes. / Nagashima, Hideo; Suzuki, Akihiro; Nobata, Mitsuharu; Aoki, Katsuyuki; Itoh, Kenji.

In: Bulletin of the Chemical Society of Japan, Vol. 71, No. 10, 01.01.1998, p. 2441-2448.

Research output: Contribution to journalArticle

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abstract = "Hydrogenation of di-, tri-, and tetranuclear ruthenium carbonyl complexes bearing guaiazulene or 4,6,8-trimethylazulene as the bridging ligand to bind the multimetallic framework was studied: [μ2 : η-guaiazuIene)Ru2(CO)5 (1a)], [μ2 : η4,6,8-trimethyIazulene)Ru2(CO)5 (1b)], [(/μ3 : η-guaiazuIene)Ru3(CO)7 (2a)], [(μ3 : η-4,6,8-trimethyIazulene)Ru3(CO)7 (2b)], [(μ3 : η-guaiazulene)Ru4(CO)9 (3a)], and [(μ3 : η-4,6,8-trimethylazulene)Ru4(CO)9 (3b)]. Reactions of these di-, tri-, and tetraruthenium complexes with dihydrogen (PH2 = 5-10 atm) at 100 °C resulted in cluster fragmentation and addition of five hydrogen atoms to the azulene ligands to form mononuclear ruthenium carbonyl hydride compounds, [(η5-pentahydroguaiazulenyl)RuH(CO)2 (4a)] or [(η5-pentahydrotrimethylazulenyl)RuH(CO)2 (4b)]. Despite potential formation of several stereoisomers dependent on the addition modes of hydrogen atoms, only one isomer of 4a or 4b was obtained in the hydrogenation. The crystal structure of a derivative of 4a revealed that the addition of hydrogen atoms occurred from the face of the azulene ligand originally bonded with the ruthenium species. Hydrogenation of the di-, tri-, and tetranuclear ruthenium complexes below 100 °C revealed that only the triruthenium compounds reacted with HZ at 50 °C via triruthenium dihydride intermediates: [(μ2 : η-tetrahydroguaiazulene)Ru3H2(CO)7 (6a)] or [(μ2 η-tetrahy-drotrimethylazulene)Ru3H2(CO)7 (6b)]; this indicates that there exists a reaction pathway to achieve facile activation of dihydrogen by the triruthenium clusters.",
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T1 - Multimetallic activation of molecular hydrogen, leading to hydrogenation of the coordinated azulenes in di-, tri-, and tetranuclear ruthenium carbonyl complexes

AU - Nagashima, Hideo

AU - Suzuki, Akihiro

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AU - Aoki, Katsuyuki

AU - Itoh, Kenji

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N2 - Hydrogenation of di-, tri-, and tetranuclear ruthenium carbonyl complexes bearing guaiazulene or 4,6,8-trimethylazulene as the bridging ligand to bind the multimetallic framework was studied: [μ2 : η-guaiazuIene)Ru2(CO)5 (1a)], [μ2 : η4,6,8-trimethyIazulene)Ru2(CO)5 (1b)], [(/μ3 : η-guaiazuIene)Ru3(CO)7 (2a)], [(μ3 : η-4,6,8-trimethyIazulene)Ru3(CO)7 (2b)], [(μ3 : η-guaiazulene)Ru4(CO)9 (3a)], and [(μ3 : η-4,6,8-trimethylazulene)Ru4(CO)9 (3b)]. Reactions of these di-, tri-, and tetraruthenium complexes with dihydrogen (PH2 = 5-10 atm) at 100 °C resulted in cluster fragmentation and addition of five hydrogen atoms to the azulene ligands to form mononuclear ruthenium carbonyl hydride compounds, [(η5-pentahydroguaiazulenyl)RuH(CO)2 (4a)] or [(η5-pentahydrotrimethylazulenyl)RuH(CO)2 (4b)]. Despite potential formation of several stereoisomers dependent on the addition modes of hydrogen atoms, only one isomer of 4a or 4b was obtained in the hydrogenation. The crystal structure of a derivative of 4a revealed that the addition of hydrogen atoms occurred from the face of the azulene ligand originally bonded with the ruthenium species. Hydrogenation of the di-, tri-, and tetranuclear ruthenium complexes below 100 °C revealed that only the triruthenium compounds reacted with HZ at 50 °C via triruthenium dihydride intermediates: [(μ2 : η-tetrahydroguaiazulene)Ru3H2(CO)7 (6a)] or [(μ2 η-tetrahy-drotrimethylazulene)Ru3H2(CO)7 (6b)]; this indicates that there exists a reaction pathway to achieve facile activation of dihydrogen by the triruthenium clusters.

AB - Hydrogenation of di-, tri-, and tetranuclear ruthenium carbonyl complexes bearing guaiazulene or 4,6,8-trimethylazulene as the bridging ligand to bind the multimetallic framework was studied: [μ2 : η-guaiazuIene)Ru2(CO)5 (1a)], [μ2 : η4,6,8-trimethyIazulene)Ru2(CO)5 (1b)], [(/μ3 : η-guaiazuIene)Ru3(CO)7 (2a)], [(μ3 : η-4,6,8-trimethyIazulene)Ru3(CO)7 (2b)], [(μ3 : η-guaiazulene)Ru4(CO)9 (3a)], and [(μ3 : η-4,6,8-trimethylazulene)Ru4(CO)9 (3b)]. Reactions of these di-, tri-, and tetraruthenium complexes with dihydrogen (PH2 = 5-10 atm) at 100 °C resulted in cluster fragmentation and addition of five hydrogen atoms to the azulene ligands to form mononuclear ruthenium carbonyl hydride compounds, [(η5-pentahydroguaiazulenyl)RuH(CO)2 (4a)] or [(η5-pentahydrotrimethylazulenyl)RuH(CO)2 (4b)]. Despite potential formation of several stereoisomers dependent on the addition modes of hydrogen atoms, only one isomer of 4a or 4b was obtained in the hydrogenation. The crystal structure of a derivative of 4a revealed that the addition of hydrogen atoms occurred from the face of the azulene ligand originally bonded with the ruthenium species. Hydrogenation of the di-, tri-, and tetranuclear ruthenium complexes below 100 °C revealed that only the triruthenium compounds reacted with HZ at 50 °C via triruthenium dihydride intermediates: [(μ2 : η-tetrahydroguaiazulene)Ru3H2(CO)7 (6a)] or [(μ2 η-tetrahy-drotrimethylazulene)Ru3H2(CO)7 (6b)]; this indicates that there exists a reaction pathway to achieve facile activation of dihydrogen by the triruthenium clusters.

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