N-O Bond Cleavage of Cluster-Coordinated Nitric Oxide Ligands Using Molecular Hydrogen

Joanne A. Smieja; Robert E. Stevens; Douglas E. Fjare; Wayne L. Gladfelter

doi:10.1021/ic00214a024

N-O Bond Cleavage of Cluster-Coordinated Nitric Oxide Ligands Using Molecular Hydrogen

Joanne A. Smieja, Robert E. Stevens, Douglas E. Fjare, Wayne L. Gladfelter

Chemistry (Twin Cities)

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

31 Scopus citations

Abstract

The reaction of several clusters containing nitric oxide ligands with molecular hydrogen has been studied. For HRu₃(CO)₁₀(NO) the products are H₂Ru₃(NH)(CO)₉, HRu₃(NH₂)(CO)₁₀, H₄Ru₄(CO)₁₂, trace amounts of H₃Ru₄(NH₂)(CO)₁₂, and a hexane-insoluble, THF-soluble precipitate. The compounds have been characterized by spectroscopy (including ¹⁵N NMR) and for HRu₃(NH₂)(CO)₁₀ by a singlercrystal X-ray crystallographic analysis (monoclinic crystal system, P2₁/a space group, a = 11.778 (3) Å, b = 11.928 (3) Å, c = 12.010 (4) Å, β = 98.54 (2)°, Z = 4). A system was built that allowed the reactions to be followed directly by high-pressure liquid chromatography. A kinetic analysis of the disappearance of HRu₃(CO)₁₀(NO) revealed that the reaction is first order in cluster concentration and is inhibited by CO. The rate also depends on the pressure of H₂, exhibiting a saturation effect above 1400 psig. The reduction of Ru₃(NOCH₃)(CO)₁₀ yields a product distribution similar to that found for HRu₃(CO)₁₀(NO) with the important exception that no hexane-insoluble species is formed. Methanol is isolated from this reaction. The major product resulting from the reduction of Ru₃(NOH)(CO)₁₀ is the same hexane-insoluble product as found for HRu₃(CO)₁₀(NO). A discussion of the mechanism of these reactions based upon the observations is presented.

Original language	English (US)
Pages (from-to)	3206-3213
Number of pages	8
Journal	Inorganic Chemistry
Volume	24
Issue number	20
DOIs	https://doi.org/10.1021/ic00214a024
State	Published - Sep 1 1985

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@article{248d93a4ed944db8b90c8d59baece2d5,

title = "N-O Bond Cleavage of Cluster-Coordinated Nitric Oxide Ligands Using Molecular Hydrogen",

abstract = "The reaction of several clusters containing nitric oxide ligands with molecular hydrogen has been studied. For HRu3(CO)10(NO) the products are H2Ru3(NH)(CO)9, HRu3(NH2)(CO)10, H4Ru4(CO)12, trace amounts of H3Ru4(NH2)(CO)12, and a hexane-insoluble, THF-soluble precipitate. The compounds have been characterized by spectroscopy (including 15N NMR) and for HRu3(NH2)(CO)10 by a singlercrystal X-ray crystallographic analysis (monoclinic crystal system, P21/a space group, a = 11.778 (3) {\AA}, b = 11.928 (3) {\AA}, c = 12.010 (4) {\AA}, β = 98.54 (2)°, Z = 4). A system was built that allowed the reactions to be followed directly by high-pressure liquid chromatography. A kinetic analysis of the disappearance of HRu3(CO)10(NO) revealed that the reaction is first order in cluster concentration and is inhibited by CO. The rate also depends on the pressure of H2, exhibiting a saturation effect above 1400 psig. The reduction of Ru3(NOCH3)(CO)10 yields a product distribution similar to that found for HRu3(CO)10(NO) with the important exception that no hexane-insoluble species is formed. Methanol is isolated from this reaction. The major product resulting from the reduction of Ru3(NOH)(CO)10 is the same hexane-insoluble product as found for HRu3(CO)10(NO). A discussion of the mechanism of these reactions based upon the observations is presented.",

author = "Smieja, {Joanne A.} and Stevens, {Robert E.} and Fjare, {Douglas E.} and Gladfelter, {Wayne L.}",

year = "1985",

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T1 - N-O Bond Cleavage of Cluster-Coordinated Nitric Oxide Ligands Using Molecular Hydrogen

AU - Smieja, Joanne A.

AU - Stevens, Robert E.

AU - Fjare, Douglas E.

AU - Gladfelter, Wayne L.

PY - 1985/9/1

Y1 - 1985/9/1

N2 - The reaction of several clusters containing nitric oxide ligands with molecular hydrogen has been studied. For HRu3(CO)10(NO) the products are H2Ru3(NH)(CO)9, HRu3(NH2)(CO)10, H4Ru4(CO)12, trace amounts of H3Ru4(NH2)(CO)12, and a hexane-insoluble, THF-soluble precipitate. The compounds have been characterized by spectroscopy (including 15N NMR) and for HRu3(NH2)(CO)10 by a singlercrystal X-ray crystallographic analysis (monoclinic crystal system, P21/a space group, a = 11.778 (3) Å, b = 11.928 (3) Å, c = 12.010 (4) Å, β = 98.54 (2)°, Z = 4). A system was built that allowed the reactions to be followed directly by high-pressure liquid chromatography. A kinetic analysis of the disappearance of HRu3(CO)10(NO) revealed that the reaction is first order in cluster concentration and is inhibited by CO. The rate also depends on the pressure of H2, exhibiting a saturation effect above 1400 psig. The reduction of Ru3(NOCH3)(CO)10 yields a product distribution similar to that found for HRu3(CO)10(NO) with the important exception that no hexane-insoluble species is formed. Methanol is isolated from this reaction. The major product resulting from the reduction of Ru3(NOH)(CO)10 is the same hexane-insoluble product as found for HRu3(CO)10(NO). A discussion of the mechanism of these reactions based upon the observations is presented.

AB - The reaction of several clusters containing nitric oxide ligands with molecular hydrogen has been studied. For HRu3(CO)10(NO) the products are H2Ru3(NH)(CO)9, HRu3(NH2)(CO)10, H4Ru4(CO)12, trace amounts of H3Ru4(NH2)(CO)12, and a hexane-insoluble, THF-soluble precipitate. The compounds have been characterized by spectroscopy (including 15N NMR) and for HRu3(NH2)(CO)10 by a singlercrystal X-ray crystallographic analysis (monoclinic crystal system, P21/a space group, a = 11.778 (3) Å, b = 11.928 (3) Å, c = 12.010 (4) Å, β = 98.54 (2)°, Z = 4). A system was built that allowed the reactions to be followed directly by high-pressure liquid chromatography. A kinetic analysis of the disappearance of HRu3(CO)10(NO) revealed that the reaction is first order in cluster concentration and is inhibited by CO. The rate also depends on the pressure of H2, exhibiting a saturation effect above 1400 psig. The reduction of Ru3(NOCH3)(CO)10 yields a product distribution similar to that found for HRu3(CO)10(NO) with the important exception that no hexane-insoluble species is formed. Methanol is isolated from this reaction. The major product resulting from the reduction of Ru3(NOH)(CO)10 is the same hexane-insoluble product as found for HRu3(CO)10(NO). A discussion of the mechanism of these reactions based upon the observations is presented.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

N-O Bond Cleavage of Cluster-Coordinated Nitric Oxide Ligands Using Molecular Hydrogen

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