Hydride participation in electron transfer processes between metal carbonyl anions and cations

Marcus J. Harrigan; Jim D. Atwood

doi:10.1021/om0304558

Hydride participation in electron transfer processes between metal carbonyl anions and cations

Marcus J. Harrigan
, Jim D. Atwood

Chemistry

SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Kinetic studies of selected metal carbonyl anions establish their reactivity as nucleophiles or for electron transfer. The iron species, [HFe(CO)₃L]^- (L = CO, PPh₃), behave as metal-centered nucleophiles when reacted with [M(CO)₆]⁺ (M = Mn, Re). Determination of the deuterium kinetic isotope ratio from kinetic studies of [HFe(CO)₄]^- and [DFe(CO)₄]^-, k_H/k_D = 2.8, indicates primary isotope effects for reaction with Mn(CO)₆⁺. Initial products from transfer of a CO and back transfer of two electrons are observed in some cases. For Re-(CO)₆⁺ exclusive formation of HRe(CO)₅ as a rhenium product strongly indicates a hydrogen transfer mechanism.

Original language	English
Pages (from-to)	846-849
Number of pages	4
Journal	Organometallics
Volume	23
Issue number	4
DOIs	https://doi.org/10.1021/om0304558
State	Published - Feb 16 2004

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title = "Hydride participation in electron transfer processes between metal carbonyl anions and cations",

abstract = "Kinetic studies of selected metal carbonyl anions establish their reactivity as nucleophiles or for electron transfer. The iron species, [HFe(CO)3L]- (L = CO, PPh3), behave as metal-centered nucleophiles when reacted with [M(CO)6]+ (M = Mn, Re). Determination of the deuterium kinetic isotope ratio from kinetic studies of [HFe(CO)4]- and [DFe(CO)4]-, kH/kD = 2.8, indicates primary isotope effects for reaction with Mn(CO)6+. Initial products from transfer of a CO and back transfer of two electrons are observed in some cases. For Re-(CO)6+ exclusive formation of HRe(CO)5 as a rhenium product strongly indicates a hydrogen transfer mechanism.",

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journal = "Organometallics",

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T1 - Hydride participation in electron transfer processes between metal carbonyl anions and cations

AU - Harrigan, Marcus J.

AU - Atwood, Jim D.

PY - 2004/2/16

Y1 - 2004/2/16

N2 - Kinetic studies of selected metal carbonyl anions establish their reactivity as nucleophiles or for electron transfer. The iron species, [HFe(CO)3L]- (L = CO, PPh3), behave as metal-centered nucleophiles when reacted with [M(CO)6]+ (M = Mn, Re). Determination of the deuterium kinetic isotope ratio from kinetic studies of [HFe(CO)4]- and [DFe(CO)4]-, kH/kD = 2.8, indicates primary isotope effects for reaction with Mn(CO)6+. Initial products from transfer of a CO and back transfer of two electrons are observed in some cases. For Re-(CO)6+ exclusive formation of HRe(CO)5 as a rhenium product strongly indicates a hydrogen transfer mechanism.

AB - Kinetic studies of selected metal carbonyl anions establish their reactivity as nucleophiles or for electron transfer. The iron species, [HFe(CO)3L]- (L = CO, PPh3), behave as metal-centered nucleophiles when reacted with [M(CO)6]+ (M = Mn, Re). Determination of the deuterium kinetic isotope ratio from kinetic studies of [HFe(CO)4]- and [DFe(CO)4]-, kH/kD = 2.8, indicates primary isotope effects for reaction with Mn(CO)6+. Initial products from transfer of a CO and back transfer of two electrons are observed in some cases. For Re-(CO)6+ exclusive formation of HRe(CO)5 as a rhenium product strongly indicates a hydrogen transfer mechanism.

UR - https://www.scopus.com/pages/publications/1442334065

U2 - 10.1021/om0304558

DO - 10.1021/om0304558

M3 - Article

AN - SCOPUS:1442334065

SN - 0276-7333

VL - 23

SP - 846

EP - 849

JO - Organometallics

JF - Organometallics

IS - 4

ER -

Hydride participation in electron transfer processes between metal carbonyl anions and cations

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