σ-CAM mechanisms for the hydrogenation of alkenes by cis- and trans- disilametallacyclic carbonyl complexes (M = Fe, Ru, Os)

Experimental and theoretical studies

Konoka Hoshi, Atsushi Tahara, Yusuke Sunada, Hironori Tsutsumi, Ryoko Inoue, Hiromasa Tanaka, Yoshihito Shiota, Kazunari Yoshizawa, Hideo Nagashima

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The hydrogenation of alkenes catalyzed by disilametallacyclic carbonyl complexes of iron, ruthenium or osmium was studied experimentally and theoretically. The disilaruthenacycle 2 with two CO ligands in the trans-configuration was prepared, characterized, and its ability to catalyze hydrogenation was studied. Similar to the corresponding iron analogue 1 in which the CO ligands are in the cis-configuration, 2 contains a H2MSi4 core with SiHSi SISHA (secondary interaction of silicon and hydrogen atoms) and catalyzed the hydrogenation of several alkenes under mild conditions. DFT calculations of 1 and 2 with cis- and trans-CO configurations (cis-1, trans-1, cis-2 and trans-2) revealed that the mechanism of ethylene hydrogenation comprises three catalytic cycles, and a key step involves the H-H bond of H2 being activated by an M-Si bond through oxidative hydrogen migration. These mechanisms are a variety of α-CAM (complex-assisted metathesis) mechanisms. Further calculations suggest that these catalytic cycles can apply to the catalytic hydrogenation of ethylene by osmium analogues of 1 and 2 (cis-3 and trans-3). Some of the elementary reactions in the cycles are dependent on the metal, and the osmium complexes show different performance from the iron and ruthenium analogues due to the characteristic natures of the third-row transition metals.

Original languageEnglish
Pages (from-to)613-626
Number of pages14
JournalBulletin of the Chemical Society of Japan
Volume90
Issue number5
DOIs
Publication statusPublished - Jan 1 2017

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Alkenes
Computer aided manufacturing
Hydrogenation
Osmium
Carbon Monoxide
Ruthenium
Iron
Hydrogen
Ligands
Silicon
Discrete Fourier transforms
Transition metals
Metals
Atoms
ethylene

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "σ-CAM mechanisms for the hydrogenation of alkenes by cis- and trans- disilametallacyclic carbonyl complexes (M = Fe, Ru, Os): Experimental and theoretical studies",
abstract = "The hydrogenation of alkenes catalyzed by disilametallacyclic carbonyl complexes of iron, ruthenium or osmium was studied experimentally and theoretically. The disilaruthenacycle 2 with two CO ligands in the trans-configuration was prepared, characterized, and its ability to catalyze hydrogenation was studied. Similar to the corresponding iron analogue 1 in which the CO ligands are in the cis-configuration, 2 contains a H2MSi4 core with SiHSi SISHA (secondary interaction of silicon and hydrogen atoms) and catalyzed the hydrogenation of several alkenes under mild conditions. DFT calculations of 1 and 2 with cis- and trans-CO configurations (cis-1, trans-1, cis-2 and trans-2) revealed that the mechanism of ethylene hydrogenation comprises three catalytic cycles, and a key step involves the H-H bond of H2 being activated by an M-Si bond through oxidative hydrogen migration. These mechanisms are a variety of α-CAM (complex-assisted metathesis) mechanisms. Further calculations suggest that these catalytic cycles can apply to the catalytic hydrogenation of ethylene by osmium analogues of 1 and 2 (cis-3 and trans-3). Some of the elementary reactions in the cycles are dependent on the metal, and the osmium complexes show different performance from the iron and ruthenium analogues due to the characteristic natures of the third-row transition metals.",
author = "Konoka Hoshi and Atsushi Tahara and Yusuke Sunada and Hironori Tsutsumi and Ryoko Inoue and Hiromasa Tanaka and Yoshihito Shiota and Kazunari Yoshizawa and Hideo Nagashima",
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T1 - σ-CAM mechanisms for the hydrogenation of alkenes by cis- and trans- disilametallacyclic carbonyl complexes (M = Fe, Ru, Os)

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AU - Hoshi, Konoka

AU - Tahara, Atsushi

AU - Sunada, Yusuke

AU - Tsutsumi, Hironori

AU - Inoue, Ryoko

AU - Tanaka, Hiromasa

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Nagashima, Hideo

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N2 - The hydrogenation of alkenes catalyzed by disilametallacyclic carbonyl complexes of iron, ruthenium or osmium was studied experimentally and theoretically. The disilaruthenacycle 2 with two CO ligands in the trans-configuration was prepared, characterized, and its ability to catalyze hydrogenation was studied. Similar to the corresponding iron analogue 1 in which the CO ligands are in the cis-configuration, 2 contains a H2MSi4 core with SiHSi SISHA (secondary interaction of silicon and hydrogen atoms) and catalyzed the hydrogenation of several alkenes under mild conditions. DFT calculations of 1 and 2 with cis- and trans-CO configurations (cis-1, trans-1, cis-2 and trans-2) revealed that the mechanism of ethylene hydrogenation comprises three catalytic cycles, and a key step involves the H-H bond of H2 being activated by an M-Si bond through oxidative hydrogen migration. These mechanisms are a variety of α-CAM (complex-assisted metathesis) mechanisms. Further calculations suggest that these catalytic cycles can apply to the catalytic hydrogenation of ethylene by osmium analogues of 1 and 2 (cis-3 and trans-3). Some of the elementary reactions in the cycles are dependent on the metal, and the osmium complexes show different performance from the iron and ruthenium analogues due to the characteristic natures of the third-row transition metals.

AB - The hydrogenation of alkenes catalyzed by disilametallacyclic carbonyl complexes of iron, ruthenium or osmium was studied experimentally and theoretically. The disilaruthenacycle 2 with two CO ligands in the trans-configuration was prepared, characterized, and its ability to catalyze hydrogenation was studied. Similar to the corresponding iron analogue 1 in which the CO ligands are in the cis-configuration, 2 contains a H2MSi4 core with SiHSi SISHA (secondary interaction of silicon and hydrogen atoms) and catalyzed the hydrogenation of several alkenes under mild conditions. DFT calculations of 1 and 2 with cis- and trans-CO configurations (cis-1, trans-1, cis-2 and trans-2) revealed that the mechanism of ethylene hydrogenation comprises three catalytic cycles, and a key step involves the H-H bond of H2 being activated by an M-Si bond through oxidative hydrogen migration. These mechanisms are a variety of α-CAM (complex-assisted metathesis) mechanisms. Further calculations suggest that these catalytic cycles can apply to the catalytic hydrogenation of ethylene by osmium analogues of 1 and 2 (cis-3 and trans-3). Some of the elementary reactions in the cycles are dependent on the metal, and the osmium complexes show different performance from the iron and ruthenium analogues due to the characteristic natures of the third-row transition metals.

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