Acceleration of CO Dissociation by a Heterometallic Center: Substitutional Reactivity of Fe2Ru(CO)12and FeRu2(CO)12

Rasul Shojaie; Jim D. Atwood

doi:10.1021/ic00261a007

Acceleration of CO Dissociation by a Heterometallic Center: Substitutional Reactivity of Fe₂Ru(CO)₁₂and FeRu₂(CO)₁₂

Rasul Shojaie
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

22 Scopus citations

Abstract

The substitutional reactivity of the mixed-metal clusters FeRu₂(CO)₁₂ and Fe₂Ru(CO)_l2has been investigated as a comparison to Fe₃(CO)_]2and Ru₃(CO)₁₂. The reactions are first order in cluster with only a very small dependence on the entering ligand (L = PPh₃ or P(OMe)₃), consistent with a dissociative interchange mechanism. The activation parameters and all other data are consistent with CO dissociation as the rate-determining step. FeRu₂(CO)₁₂undergoes substitution to FeRu₂(CO)₁₀L₂(both ligands substituted on ruthenium) with no evidence for a monosubstituted cluster. Substitution on Fe₂Ru(CO)₁₂leads initially to Fe₂Ru(CO)₁₁L (substitution on ruthenium) and subsequently to Fe₂Ru(CO)₁₀L₂ (substitution on iron and ruthenium). CO dissociation from Fe₂Ru(CO)₁₂and FeRu₂(CO)₁₂occurs more rapidly than from Fe₃(CO)₁₂or from Ru₃(CO)₁₂, suggesting a metal center effect on CO dissociation.

Original language	English
Pages (from-to)	2199-2201
Number of pages	3
Journal	Inorganic Chemistry
Volume	26
Issue number	14
DOIs	https://doi.org/10.1021/ic00261a007
State	Published - 1987

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@article{50472052256d495f99135ab1c6d1142e,

title = "Acceleration of CO Dissociation by a Heterometallic Center: Substitutional Reactivity of Fe2Ru(CO)12and FeRu2(CO)12",

abstract = "The substitutional reactivity of the mixed-metal clusters FeRu2(CO)12 and Fe2Ru(CO)l2has been investigated as a comparison to Fe3(CO)]2and Ru3(CO)12. The reactions are first order in cluster with only a very small dependence on the entering ligand (L = PPh3 or P(OMe)3), consistent with a dissociative interchange mechanism. The activation parameters and all other data are consistent with CO dissociation as the rate-determining step. FeRu2(CO)12undergoes substitution to FeRu2(CO)10L2(both ligands substituted on ruthenium) with no evidence for a monosubstituted cluster. Substitution on Fe2Ru(CO)12leads initially to Fe2Ru(CO)11L (substitution on ruthenium) and subsequently to Fe2Ru(CO)10L2 (substitution on iron and ruthenium). CO dissociation from Fe2Ru(CO)12and FeRu2(CO)12occurs more rapidly than from Fe3(CO)12or from Ru3(CO)12, suggesting a metal center effect on CO dissociation.",

author = "Rasul Shojaie and Atwood, \{Jim D.\}",

year = "1987",

doi = "10.1021/ic00261a007",

language = "English",

volume = "26",

pages = "2199--2201",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Acceleration of CO Dissociation by a Heterometallic Center

T2 - Substitutional Reactivity of Fe2Ru(CO)12and FeRu2(CO)12

AU - Shojaie, Rasul

AU - Atwood, Jim D.

PY - 1987

Y1 - 1987

N2 - The substitutional reactivity of the mixed-metal clusters FeRu2(CO)12 and Fe2Ru(CO)l2has been investigated as a comparison to Fe3(CO)]2and Ru3(CO)12. The reactions are first order in cluster with only a very small dependence on the entering ligand (L = PPh3 or P(OMe)3), consistent with a dissociative interchange mechanism. The activation parameters and all other data are consistent with CO dissociation as the rate-determining step. FeRu2(CO)12undergoes substitution to FeRu2(CO)10L2(both ligands substituted on ruthenium) with no evidence for a monosubstituted cluster. Substitution on Fe2Ru(CO)12leads initially to Fe2Ru(CO)11L (substitution on ruthenium) and subsequently to Fe2Ru(CO)10L2 (substitution on iron and ruthenium). CO dissociation from Fe2Ru(CO)12and FeRu2(CO)12occurs more rapidly than from Fe3(CO)12or from Ru3(CO)12, suggesting a metal center effect on CO dissociation.

AB - The substitutional reactivity of the mixed-metal clusters FeRu2(CO)12 and Fe2Ru(CO)l2has been investigated as a comparison to Fe3(CO)]2and Ru3(CO)12. The reactions are first order in cluster with only a very small dependence on the entering ligand (L = PPh3 or P(OMe)3), consistent with a dissociative interchange mechanism. The activation parameters and all other data are consistent with CO dissociation as the rate-determining step. FeRu2(CO)12undergoes substitution to FeRu2(CO)10L2(both ligands substituted on ruthenium) with no evidence for a monosubstituted cluster. Substitution on Fe2Ru(CO)12leads initially to Fe2Ru(CO)11L (substitution on ruthenium) and subsequently to Fe2Ru(CO)10L2 (substitution on iron and ruthenium). CO dissociation from Fe2Ru(CO)12and FeRu2(CO)12occurs more rapidly than from Fe3(CO)12or from Ru3(CO)12, suggesting a metal center effect on CO dissociation.

UR - https://www.scopus.com/pages/publications/24844433877

U2 - 10.1021/ic00261a007

DO - 10.1021/ic00261a007

M3 - Article

AN - SCOPUS:24844433877

SN - 0020-1669

VL - 26

SP - 2199

EP - 2201

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 14

ER -

Acceleration of CO Dissociation by a Heterometallic Center: Substitutional Reactivity of Fe₂Ru(CO)₁₂and FeRu₂(CO)₁₂

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