Photocatalysis of cyclooctane dehydrogenation by the A-frame dinuclear rhodium complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane]

Hiroaki Itagaki, Hisahiro Einaga, Yasukazu Saito

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7 Citations (Scopus)

Abstract

Visible-light irradiation at the longest-wavelength absorption band (λmax = 475 nm) of the A-frame dinuclear complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane] caused catalytic dehydrogenation of cyclooctane [initial turnover frequency = 32.8 h-1, total turnover number = 27.3 (per complex)]. The absorption band effective for photocatalysis was assigned to a metal-to-ligand charge transfer (m.l.c.t.) by extended Hückel molecular orbital (EHMO) calculations. The m.l.c.t. transition energy of [Rh2(μ-S)(CO)2(dppm)2] was lower than that of the photocatalytically active mononuclear complex [RhCl(CO)(PPh3)2] (λmax = 364 nm), the origin of which was investigated in detail in terms of the Rh-Rh and Rh-S interactions.

Original languageEnglish
Pages (from-to)1689-1693
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number11
DOIs
Publication statusPublished - Dec 1 1993
Externally publishedYes

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Rhodium
Photocatalysis
Methane
Dehydrogenation
Carbon Monoxide
Charge transfer
Absorption spectra
Metals
Ligands
Orbital calculations
Molecular orbitals
Electron transitions
Irradiation
Wavelength
cyclooctane

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "Photocatalysis of cyclooctane dehydrogenation by the A-frame dinuclear rhodium complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane]",
abstract = "Visible-light irradiation at the longest-wavelength absorption band (λmax = 475 nm) of the A-frame dinuclear complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane] caused catalytic dehydrogenation of cyclooctane [initial turnover frequency = 32.8 h-1, total turnover number = 27.3 (per complex)]. The absorption band effective for photocatalysis was assigned to a metal-to-ligand charge transfer (m.l.c.t.) by extended H{\"u}ckel molecular orbital (EHMO) calculations. The m.l.c.t. transition energy of [Rh2(μ-S)(CO)2(dppm)2] was lower than that of the photocatalytically active mononuclear complex [RhCl(CO)(PPh3)2] (λmax = 364 nm), the origin of which was investigated in detail in terms of the Rh-Rh and Rh-S interactions.",
author = "Hiroaki Itagaki and Hisahiro Einaga and Yasukazu Saito",
year = "1993",
month = "12",
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journal = "Dalton Transactions",
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T1 - Photocatalysis of cyclooctane dehydrogenation by the A-frame dinuclear rhodium complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane]

AU - Itagaki, Hiroaki

AU - Einaga, Hisahiro

AU - Saito, Yasukazu

PY - 1993/12/1

Y1 - 1993/12/1

N2 - Visible-light irradiation at the longest-wavelength absorption band (λmax = 475 nm) of the A-frame dinuclear complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane] caused catalytic dehydrogenation of cyclooctane [initial turnover frequency = 32.8 h-1, total turnover number = 27.3 (per complex)]. The absorption band effective for photocatalysis was assigned to a metal-to-ligand charge transfer (m.l.c.t.) by extended Hückel molecular orbital (EHMO) calculations. The m.l.c.t. transition energy of [Rh2(μ-S)(CO)2(dppm)2] was lower than that of the photocatalytically active mononuclear complex [RhCl(CO)(PPh3)2] (λmax = 364 nm), the origin of which was investigated in detail in terms of the Rh-Rh and Rh-S interactions.

AB - Visible-light irradiation at the longest-wavelength absorption band (λmax = 475 nm) of the A-frame dinuclear complex [Rh2(μ-S)(CO)2(dppm)2] [dppm = bis(diphenylphosphino)methane] caused catalytic dehydrogenation of cyclooctane [initial turnover frequency = 32.8 h-1, total turnover number = 27.3 (per complex)]. The absorption band effective for photocatalysis was assigned to a metal-to-ligand charge transfer (m.l.c.t.) by extended Hückel molecular orbital (EHMO) calculations. The m.l.c.t. transition energy of [Rh2(μ-S)(CO)2(dppm)2] was lower than that of the photocatalytically active mononuclear complex [RhCl(CO)(PPh3)2] (λmax = 364 nm), the origin of which was investigated in detail in terms of the Rh-Rh and Rh-S interactions.

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