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Title: Photochemical oxidative addition reactions of (eta/sup 5/-cyclopentadienyl)bis(ethene)rhodium with dihydrogen and trialkylsilanes: formation and isolation of rhodium(III) and rhodium(V) hydrides

Abstract

Photolysis of CpRh(C/sub 2/H/sub 4/)/sub 2/ (1; Cp = eta/sup 5/-C/sub 5/H/sub 5/) in benzene or toluene in the presence of R/sub 3/SiH (R = Me, Et) yields CpRh/sup III/(C/sub 2/H/sub 4/)(SiEt/sub 3/)H (2), CpRh/sup V/(SiEt/sub 3/)/sub 2/(H)/sub 2/ (3), ethane, and triethylsilane. By appropriate choice of conditions the reaction can be controlled to enable the isolation of either 2 or 3. The identification of 2 and 3 are secured by multinuclear NMR. Photolysis of 1 in liquid xenon at 170 K under a 10-bar pressure of hydrogen yields CpRh(C/sub 2/H/sub 4/)(H)/sub 2/ (4). Complex 4 and several /sup 2/H-substituted analogues are identified by FTIR spectroscopy. 4 may be converted to CpRh(C/sub 2/H/sub 4/)(D)/sub 2/ by photolysis under D/sub 2/. Ethane is generated in a slow thermal process subsequent to photolysis that may be followed by FTIR or NMR spectroscopy in liquid xenon. The dihydride 4 has not been detected by NMR when 1 is photolyzed in toluene solution or LXe under lower hydrogen pressures, even though ethane is generated.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Univ. of York, (England)
OSTI Identifier:
7190543
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 7:7
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CYCLOALKENES; OXIDATION; PHOTOCHEMICAL REACTIONS; HYDROGEN; RHODIUM COMPOUNDS; SILANES; EXPERIMENTAL DATA; NUCLEAR MAGNETIC RESONANCE; PHOTOCHEMISTRY; ALKENES; CHEMICAL REACTIONS; CHEMISTRY; DATA; ELEMENTS; HYDRIDES; HYDROCARBONS; HYDROGEN COMPOUNDS; INFORMATION; MAGNETIC RESONANCE; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC SILICON COMPOUNDS; REFRACTORY METAL COMPOUNDS; RESONANCE; SILICON COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; 400500* - Photochemistry

Citation Formats

Duckett, S B, Haddleton, D M, Jackson, S A, Perutz, R N, Poliakoff, M, and Upmacis, R K. Photochemical oxidative addition reactions of (eta/sup 5/-cyclopentadienyl)bis(ethene)rhodium with dihydrogen and trialkylsilanes: formation and isolation of rhodium(III) and rhodium(V) hydrides. United States: N. p., 1988. Web. doi:10.1021/om00097a013.
Duckett, S B, Haddleton, D M, Jackson, S A, Perutz, R N, Poliakoff, M, & Upmacis, R K. Photochemical oxidative addition reactions of (eta/sup 5/-cyclopentadienyl)bis(ethene)rhodium with dihydrogen and trialkylsilanes: formation and isolation of rhodium(III) and rhodium(V) hydrides. United States. https://doi.org/10.1021/om00097a013
Duckett, S B, Haddleton, D M, Jackson, S A, Perutz, R N, Poliakoff, M, and Upmacis, R K. 1988. "Photochemical oxidative addition reactions of (eta/sup 5/-cyclopentadienyl)bis(ethene)rhodium with dihydrogen and trialkylsilanes: formation and isolation of rhodium(III) and rhodium(V) hydrides". United States. https://doi.org/10.1021/om00097a013.
@article{osti_7190543,
title = {Photochemical oxidative addition reactions of (eta/sup 5/-cyclopentadienyl)bis(ethene)rhodium with dihydrogen and trialkylsilanes: formation and isolation of rhodium(III) and rhodium(V) hydrides},
author = {Duckett, S B and Haddleton, D M and Jackson, S A and Perutz, R N and Poliakoff, M and Upmacis, R K},
abstractNote = {Photolysis of CpRh(C/sub 2/H/sub 4/)/sub 2/ (1; Cp = eta/sup 5/-C/sub 5/H/sub 5/) in benzene or toluene in the presence of R/sub 3/SiH (R = Me, Et) yields CpRh/sup III/(C/sub 2/H/sub 4/)(SiEt/sub 3/)H (2), CpRh/sup V/(SiEt/sub 3/)/sub 2/(H)/sub 2/ (3), ethane, and triethylsilane. By appropriate choice of conditions the reaction can be controlled to enable the isolation of either 2 or 3. The identification of 2 and 3 are secured by multinuclear NMR. Photolysis of 1 in liquid xenon at 170 K under a 10-bar pressure of hydrogen yields CpRh(C/sub 2/H/sub 4/)(H)/sub 2/ (4). Complex 4 and several /sup 2/H-substituted analogues are identified by FTIR spectroscopy. 4 may be converted to CpRh(C/sub 2/H/sub 4/)(D)/sub 2/ by photolysis under D/sub 2/. Ethane is generated in a slow thermal process subsequent to photolysis that may be followed by FTIR or NMR spectroscopy in liquid xenon. The dihydride 4 has not been detected by NMR when 1 is photolyzed in toluene solution or LXe under lower hydrogen pressures, even though ethane is generated.},
doi = {10.1021/om00097a013},
url = {https://www.osti.gov/biblio/7190543}, journal = {Organometallics; (United States)},
number = ,
volume = 7:7,
place = {United States},
year = {Fri Jul 01 00:00:00 EDT 1988},
month = {Fri Jul 01 00:00:00 EDT 1988}
}