Ni23Se12(PEt3)13. An Intramolecular Intergrowth of NiSe and Ni

J. G. Brennan; T. Siegrist; Y. U. Kwon; S. M. Stuczynski; M. L. Steigerwald

doi:10.1021/ja00052a034

Ni₂₃Se₁₂(PEt₃)₁₃. An Intramolecular Intergrowth of NiSe and Ni

J. G. Brennan, T. Siegrist, Y. U. Kwon, S. M. Stuczynski, M. L. Steigerwald

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Abstract

The reaction of Ni(COD)₂(COD = cyclooctadiene) with Et₃PSe at elevated temperature gives a mixture of Ni₃Se₂ and elemental Ni. When the same reagents are combined at lower temperature the cluster compound Ni₂₃Se₁₂(PEt₃)₁₃ is formed and can be isolated as a crystalline solid. We have determined the structure of this compound crystallographically (trigonal space group R3c, a = 17.577 (1) Å, c = 75.191 (6) Å, V = 20118 Å³, Z = 6). The crystallography shows the cluster to be a fusion of distorted fragments of NiSe (NiAs structure type) and hexagonally close packed elemental Ni. This cluster can be converted thermally to the same solid products (Ni₃Se₂ and Ni) as those resulting from the combination of Ni⁰and Se⁰ under the more forcing conditions. This shows that the cluster is allowable as an intermediate in the molecules-to-solids conversion.

Original language	English (US)
Pages (from-to)	10334-10338
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	114
Issue number	26
DOIs	https://doi.org/10.1021/ja00052a034
State	Published - Dec 1 1992
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00052a034

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title = "Ni23Se12(PEt3)13. An Intramolecular Intergrowth of NiSe and Ni",

abstract = "The reaction of Ni(COD)2(COD = cyclooctadiene) with Et3PSe at elevated temperature gives a mixture of Ni3Se2 and elemental Ni. When the same reagents are combined at lower temperature the cluster compound Ni23Se12(PEt3)13 is formed and can be isolated as a crystalline solid. We have determined the structure of this compound crystallographically (trigonal space group R3c, a = 17.577 (1) {\AA}, c = 75.191 (6) {\AA}, V = 20118 {\AA}3, Z = 6). The crystallography shows the cluster to be a fusion of distorted fragments of NiSe (NiAs structure type) and hexagonally close packed elemental Ni. This cluster can be converted thermally to the same solid products (Ni3Se2 and Ni) as those resulting from the combination of Ni0and Se0 under the more forcing conditions. This shows that the cluster is allowable as an intermediate in the molecules-to-solids conversion.",

author = "Brennan, {J. G.} and T. Siegrist and Kwon, {Y. U.} and Stuczynski, {S. M.} and Steigerwald, {M. L.}",

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T1 - Ni23Se12(PEt3)13. An Intramolecular Intergrowth of NiSe and Ni

AU - Brennan, J. G.

AU - Siegrist, T.

AU - Kwon, Y. U.

AU - Stuczynski, S. M.

AU - Steigerwald, M. L.

PY - 1992/12/1

Y1 - 1992/12/1

N2 - The reaction of Ni(COD)2(COD = cyclooctadiene) with Et3PSe at elevated temperature gives a mixture of Ni3Se2 and elemental Ni. When the same reagents are combined at lower temperature the cluster compound Ni23Se12(PEt3)13 is formed and can be isolated as a crystalline solid. We have determined the structure of this compound crystallographically (trigonal space group R3c, a = 17.577 (1) Å, c = 75.191 (6) Å, V = 20118 Å3, Z = 6). The crystallography shows the cluster to be a fusion of distorted fragments of NiSe (NiAs structure type) and hexagonally close packed elemental Ni. This cluster can be converted thermally to the same solid products (Ni3Se2 and Ni) as those resulting from the combination of Ni0and Se0 under the more forcing conditions. This shows that the cluster is allowable as an intermediate in the molecules-to-solids conversion.

AB - The reaction of Ni(COD)2(COD = cyclooctadiene) with Et3PSe at elevated temperature gives a mixture of Ni3Se2 and elemental Ni. When the same reagents are combined at lower temperature the cluster compound Ni23Se12(PEt3)13 is formed and can be isolated as a crystalline solid. We have determined the structure of this compound crystallographically (trigonal space group R3c, a = 17.577 (1) Å, c = 75.191 (6) Å, V = 20118 Å3, Z = 6). The crystallography shows the cluster to be a fusion of distorted fragments of NiSe (NiAs structure type) and hexagonally close packed elemental Ni. This cluster can be converted thermally to the same solid products (Ni3Se2 and Ni) as those resulting from the combination of Ni0and Se0 under the more forcing conditions. This shows that the cluster is allowable as an intermediate in the molecules-to-solids conversion.

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Ni₂₃Se₁₂(PEt₃)₁₃. An Intramolecular Intergrowth of NiSe and Ni

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