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Title: Kinetics of the reduction of Co (o-phen){sub 3}{sup 3+} by the metal carbonyl anions Re (CO){sub 5}{sup {minus}}, Mn(CO){sub 4}L{sup {minus}} (L = CO, PEt{sub 3}, PBu{sub 3}, PPH{sub 3}), Co(CO){sub 4}{sup {minus}}, CpMo(CO){sub 3}{sup {minus}}, and CpFe(CO){sub 2}{sup {minus}} (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, o-phen = o-Phenanthroline). Structural determinations of [PPN{sup +}][Mn(CO){sub 5}{sup {minus}}] and [PPN{sup +}][Mn(CO){sub 4}(PEt{sub 3}){sup {minus}}]{lg_bullet}THF

Abstract

Reaction of metal carbonyl anions, [M{sup {minus}}], with M{sup prime}(o-phen){sub 3}{sup 3+} (M{sup {prime}}=Fe,Co) results in electron transfer giving metal carbonyl dimers and M(o-phen){sub 3}{sup 2+}. The rate depends on the concentration of M{sup prime}(o-phen){sub 3}{sup 3+} and on [M{sup {minus}}]. Fe(o-phen){sub 3}{sup 3+} reacts much more rapidly than does Co(o-phen){sub 3}{sup 3+}, consistent with expectations for an outer-sphere electron-transfer process. Dependence on the nature of the metal carbonyl anions is also consistent with outer-sphere electron transfer. Reaction of the metal carbonyl anions with 3-acet-oxy-N-methylpyridinium tetrafluoroborate is also used to show the outer-sphere rectivity of the metal carbonyl anions. Structures of the PPN{sup +} salts of the Mn(CO){sub 4}L{sup {minus}} anions(L=CO and PEt{sub 3}) are reported as a possible means to assess intrinsic barriers. 27 refs., 2 figs., 7 tabs.

Authors:
; ;  [1]
  1. Univ. of Buffalo, NY (United States) [and others
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
263713
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Other Information: PBD: Jan 1992
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; COBALT COMPLEXES; REDUCTION; RHENIUM COMPLEXES; OXIDATION; MANGANESE COMPLEXES; MOLYBDENUM COMPLEXES; IRON COMPLEXES; CHEMICAL REACTION KINETICS; ORGANOMETALLIC COMPOUNDS; CRYSTAL STRUCTURE

Citation Formats

Corraine, M.S., Lai, C.K., and Zhen, Y.. Kinetics of the reduction of Co (o-phen){sub 3}{sup 3+} by the metal carbonyl anions Re (CO){sub 5}{sup {minus}}, Mn(CO){sub 4}L{sup {minus}} (L = CO, PEt{sub 3}, PBu{sub 3}, PPH{sub 3}), Co(CO){sub 4}{sup {minus}}, CpMo(CO){sub 3}{sup {minus}}, and CpFe(CO){sub 2}{sup {minus}} (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, o-phen = o-Phenanthroline). Structural determinations of [PPN{sup +}][Mn(CO){sub 5}{sup {minus}}] and [PPN{sup +}][Mn(CO){sub 4}(PEt{sub 3}){sup {minus}}]{lg_bullet}THF. United States: N. p., 1992. Web. doi:10.1021/om00037a014.
Corraine, M.S., Lai, C.K., & Zhen, Y.. Kinetics of the reduction of Co (o-phen){sub 3}{sup 3+} by the metal carbonyl anions Re (CO){sub 5}{sup {minus}}, Mn(CO){sub 4}L{sup {minus}} (L = CO, PEt{sub 3}, PBu{sub 3}, PPH{sub 3}), Co(CO){sub 4}{sup {minus}}, CpMo(CO){sub 3}{sup {minus}}, and CpFe(CO){sub 2}{sup {minus}} (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, o-phen = o-Phenanthroline). Structural determinations of [PPN{sup +}][Mn(CO){sub 5}{sup {minus}}] and [PPN{sup +}][Mn(CO){sub 4}(PEt{sub 3}){sup {minus}}]{lg_bullet}THF. United States. doi:10.1021/om00037a014.
Corraine, M.S., Lai, C.K., and Zhen, Y.. Wed . "Kinetics of the reduction of Co (o-phen){sub 3}{sup 3+} by the metal carbonyl anions Re (CO){sub 5}{sup {minus}}, Mn(CO){sub 4}L{sup {minus}} (L = CO, PEt{sub 3}, PBu{sub 3}, PPH{sub 3}), Co(CO){sub 4}{sup {minus}}, CpMo(CO){sub 3}{sup {minus}}, and CpFe(CO){sub 2}{sup {minus}} (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, o-phen = o-Phenanthroline). Structural determinations of [PPN{sup +}][Mn(CO){sub 5}{sup {minus}}] and [PPN{sup +}][Mn(CO){sub 4}(PEt{sub 3}){sup {minus}}]{lg_bullet}THF". United States. doi:10.1021/om00037a014.
@article{osti_263713,
title = {Kinetics of the reduction of Co (o-phen){sub 3}{sup 3+} by the metal carbonyl anions Re (CO){sub 5}{sup {minus}}, Mn(CO){sub 4}L{sup {minus}} (L = CO, PEt{sub 3}, PBu{sub 3}, PPH{sub 3}), Co(CO){sub 4}{sup {minus}}, CpMo(CO){sub 3}{sup {minus}}, and CpFe(CO){sub 2}{sup {minus}} (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, o-phen = o-Phenanthroline). Structural determinations of [PPN{sup +}][Mn(CO){sub 5}{sup {minus}}] and [PPN{sup +}][Mn(CO){sub 4}(PEt{sub 3}){sup {minus}}]{lg_bullet}THF},
author = {Corraine, M.S. and Lai, C.K. and Zhen, Y.},
abstractNote = {Reaction of metal carbonyl anions, [M{sup {minus}}], with M{sup prime}(o-phen){sub 3}{sup 3+} (M{sup {prime}}=Fe,Co) results in electron transfer giving metal carbonyl dimers and M(o-phen){sub 3}{sup 2+}. The rate depends on the concentration of M{sup prime}(o-phen){sub 3}{sup 3+} and on [M{sup {minus}}]. Fe(o-phen){sub 3}{sup 3+} reacts much more rapidly than does Co(o-phen){sub 3}{sup 3+}, consistent with expectations for an outer-sphere electron-transfer process. Dependence on the nature of the metal carbonyl anions is also consistent with outer-sphere electron transfer. Reaction of the metal carbonyl anions with 3-acet-oxy-N-methylpyridinium tetrafluoroborate is also used to show the outer-sphere rectivity of the metal carbonyl anions. Structures of the PPN{sup +} salts of the Mn(CO){sub 4}L{sup {minus}} anions(L=CO and PEt{sub 3}) are reported as a possible means to assess intrinsic barriers. 27 refs., 2 figs., 7 tabs.},
doi = {10.1021/om00037a014},
journal = {Organometallics},
number = 1,
volume = 11,
place = {United States},
year = {1992},
month = {1}
}