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Title: (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)

Abstract

We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

Authors:
Publication Date:
Research Org.:
State Univ. of New York, Buffalo, NY (United States). Research Foundation
Sponsoring Org.:
USDOE; USDOE, Washington, DC (United States)
OSTI Identifier:
5573799
Report Number(s):
DOE/ER/13775-3
ON: DE92012539
DOE Contract Number:
FG02-87ER13775
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ORGANOMETALLIC COMPOUNDS; CHARGE EXCHANGE; ELECTRON TRANSFER; ANIONS; CARBON MONOXIDE LASERS; CARBONYLS; INFRARED SPECTROMETERS; LIQUID FLOW; PROGRESS REPORT; CHARGED PARTICLES; DOCUMENT TYPES; FLUID FLOW; GAS LASERS; IONS; LASERS; MEASURING INSTRUMENTS; ORGANIC COMPOUNDS; SPECTROMETERS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Atwood, J. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report). United States: N. p., 1990. Web. doi:10.2172/5573799.
Atwood, J. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report). United States. doi:10.2172/5573799.
Atwood, J. Mon . "(Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)". United States. doi:10.2172/5573799. https://www.osti.gov/servlets/purl/5573799.
@article{osti_5573799,
title = {(Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)},
author = {Atwood, J.},
abstractNote = {We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.},
doi = {10.2172/5573799},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 1990},
month = {Mon Jan 01 00:00:00 EST 1990}
}

Technical Report:

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  • We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.
  • During the course of Grant ER13775 we have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. The spectrometer combined conventional stopped-flow techniques with an infrared optical system comprised of a carbon monoxide laser, an IRTRAN flow-through cell and a mercury-cadium-telluride detector. In this summary we will highlight our results on reactions: (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve additional of an electron to, or removal of an electron from organometallic complexes that containmore » a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions. 12 refs.« less
  • Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO{sup 2+} transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possiblymore » through a ring-slippage mechanism.« less
  • Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO{sup 2+} transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possiblymore » through a ring-slippage mechanism.« less
  • During 1994, despite the disruptions, the authors have made progress in several aspects of their research on electron transfer reactions between organometallic complexes. This summary covers three areas that are relatively complete: (1) reactions between metal carbonyl anions and metal carbonyl halides, (2) reactions of hydrido- and alkyl-containing anions (RFe(CO){sup {minus}}{sub 4} and RW (CO){sub 5}{sup {minus}}) with metal carbonyl cations and (3) reactions of a seventeen-electron complex (Cp{asterisk}Cr(CO){sub 3}{lg_bullet}) with metal carbonyl derivatives. Two areas of examination that have just begun (possible carbene transfer and the possible role of metal carbonyl anions in carbon-hydrogen bond activation) will also bemore » described.« less