Surface Organometallic Chemistry: Formation of the Grafted Anionic Clusters [HFeOs3(CO)13]-, [HFeRu3(CO)13]-, and [FeCo3(CO)12]-on a Hydroxylated Magnesia

Agnes Choplin; Lin Huang; Jean Marie Basset; Rene Mathieu; Upali Siriwardane; Sheldon G. Shore

doi:10.1021/om00139a007

Surface Organometallic Chemistry: Formation of the Grafted Anionic Clusters [HFeOs₃(CO)₁₃]^-, [HFeRu₃(CO)₁₃]^-, and [FeCo₃(CO)₁₂]^-on a Hydroxylated Magnesia

Agnes Choplin^*, Lin Huang, Jean Marie Basset, Rene Mathieu, Upali Siriwardane, Sheldon G. Shore

^*Corresponding author for this work

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Abstract

The reaction of the mixed hydrido carbonyl H₂FeM₃(CO)₁₃ (M = Ru, Os) and HFeCo₃(CO)₁₂ with the surface of partially hydroxylated magnesia has been studied in situ by IR spectroscopy, evolution of gases, and extraction of the adsorbed complexes. At room temperature, H₂FeM₃(CO)₁₃ (M = Ru, Os) and HFeCo₃(CO)₁₂ are deprotonated at the surface of magnesia to give the anions [HFeM₃(CO)₁₃]^- (M = Ru, Os) and [FeCo₃(CO)₁₂]^- with virtually no disproportionation to other cluster species. The anions [HFeM₃(CO)₁₃]^- (M = Ru, Os) were also synthesized by proton abstraction by KOH and by KH. It is suggested that on the surface of the magnesia the deprotonation occurs via surface OH groups. From IR spectra apparently there is no tight ion pair between the anions on the surface and the Lewis centers which is in contrast with that which is observed for [HFe₃(CO)₁₁]^- (M = Fe). A mechanistic explanation is proposed. Thermal decomposition of the surface-bound anions has been studied.

Original language	English (US)
Pages (from-to)	1547-1551
Number of pages	5
Journal	Organometallics
Volume	5
Issue number	8
DOIs	https://doi.org/10.1021/om00139a007
State	Published - 1986
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Surface Organometallic Chemistry: Formation of the Grafted Anionic Clusters [HFeOs3(CO)13]-, [HFeRu3(CO)13]-, and [FeCo3(CO)12]-on a Hydroxylated Magnesia",

abstract = "The reaction of the mixed hydrido carbonyl H2FeM3(CO)13 (M = Ru, Os) and HFeCo3(CO)12 with the surface of partially hydroxylated magnesia has been studied in situ by IR spectroscopy, evolution of gases, and extraction of the adsorbed complexes. At room temperature, H2FeM3(CO)13 (M = Ru, Os) and HFeCo3(CO)12 are deprotonated at the surface of magnesia to give the anions [HFeM3(CO)13]- (M = Ru, Os) and [FeCo3(CO)12]- with virtually no disproportionation to other cluster species. The anions [HFeM3(CO)13]- (M = Ru, Os) were also synthesized by proton abstraction by KOH and by KH. It is suggested that on the surface of the magnesia the deprotonation occurs via surface OH groups. From IR spectra apparently there is no tight ion pair between the anions on the surface and the Lewis centers which is in contrast with that which is observed for [HFe3(CO)11]- (M = Fe). A mechanistic explanation is proposed. Thermal decomposition of the surface-bound anions has been studied.",

author = "Agnes Choplin and Lin Huang and Basset, {Jean Marie} and Rene Mathieu and Upali Siriwardane and Shore, {Sheldon G.}",

year = "1986",

doi = "10.1021/om00139a007",

language = "English (US)",

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pages = "1547--1551",

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T1 - Surface Organometallic Chemistry

T2 - Formation of the Grafted Anionic Clusters [HFeOs3(CO)13]-, [HFeRu3(CO)13]-, and [FeCo3(CO)12]-on a Hydroxylated Magnesia

AU - Choplin, Agnes

AU - Huang, Lin

AU - Basset, Jean Marie

AU - Mathieu, Rene

AU - Siriwardane, Upali

AU - Shore, Sheldon G.

PY - 1986

Y1 - 1986

N2 - The reaction of the mixed hydrido carbonyl H2FeM3(CO)13 (M = Ru, Os) and HFeCo3(CO)12 with the surface of partially hydroxylated magnesia has been studied in situ by IR spectroscopy, evolution of gases, and extraction of the adsorbed complexes. At room temperature, H2FeM3(CO)13 (M = Ru, Os) and HFeCo3(CO)12 are deprotonated at the surface of magnesia to give the anions [HFeM3(CO)13]- (M = Ru, Os) and [FeCo3(CO)12]- with virtually no disproportionation to other cluster species. The anions [HFeM3(CO)13]- (M = Ru, Os) were also synthesized by proton abstraction by KOH and by KH. It is suggested that on the surface of the magnesia the deprotonation occurs via surface OH groups. From IR spectra apparently there is no tight ion pair between the anions on the surface and the Lewis centers which is in contrast with that which is observed for [HFe3(CO)11]- (M = Fe). A mechanistic explanation is proposed. Thermal decomposition of the surface-bound anions has been studied.

AB - The reaction of the mixed hydrido carbonyl H2FeM3(CO)13 (M = Ru, Os) and HFeCo3(CO)12 with the surface of partially hydroxylated magnesia has been studied in situ by IR spectroscopy, evolution of gases, and extraction of the adsorbed complexes. At room temperature, H2FeM3(CO)13 (M = Ru, Os) and HFeCo3(CO)12 are deprotonated at the surface of magnesia to give the anions [HFeM3(CO)13]- (M = Ru, Os) and [FeCo3(CO)12]- with virtually no disproportionation to other cluster species. The anions [HFeM3(CO)13]- (M = Ru, Os) were also synthesized by proton abstraction by KOH and by KH. It is suggested that on the surface of the magnesia the deprotonation occurs via surface OH groups. From IR spectra apparently there is no tight ion pair between the anions on the surface and the Lewis centers which is in contrast with that which is observed for [HFe3(CO)11]- (M = Fe). A mechanistic explanation is proposed. Thermal decomposition of the surface-bound anions has been studied.

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Surface Organometallic Chemistry: Formation of the Grafted Anionic Clusters [HFeOs₃(CO)₁₃]^-, [HFeRu₃(CO)₁₃]^-, and [FeCo₃(CO)₁₂]^-on a Hydroxylated Magnesia

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