Cluster Condensation by Thermolysis: Synthesis of a Rhomb-Linked Re12Se16 Dicluster and Factors Relevant to the Formation of the Re24Se32 Tetracluster

Zhiping Zheng, R. H. Holm

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Abstract

The cluster cis-[Re6Se8(PEt3)4I2] undergoes substitution reactions with neutral ligands L in the presence of AgSbF6 to afford the cis-disubstituted clusters [Re2Se8(PEt3)4L2] 2+(L = MeCN (6), t-BuCN, DMF, Me2SO (9)). Cluster 6 reacts with pyridine to give [Re6Se8(PEt3)4(py)2] 2+. Retention of stereochemistry was demonstrated from 31P NMR spectra and the crystal structure of [9](SbF6)2, which revealed the two Me2SO ligands to be O-bonded at adjacent Re sites of the face-capped octahedral [Re6(μ-Se)8]2+ core. The clusters cis-[Re6Se8(PEt3)4L 2]2+ are of interest as possible precursors to oligomeric clusters under thermolysis conditions where one or both ligands L are removed. Thermolysis of orange-red [6](SbF6)2 (180°C, 24 h) afforded a brown-green crystalline product identified by an X-ray structure determination to contain the dicluster [Re12Se16(PEt3)8(MeCN) 2]4+ (11). Two [Re6Se8]2+ cluster units are bridged by a Re2Se2 rhomb to afford the centrosymmetric core [Re123-Se)144Se) 2]4+, established recently for the dicluster [Re12Se16(PEt3)10]4+. The two acetonitrile ligands occur in a trans orientation on the two cluster units. From consideration of the crystal structure of the precursor compound [6](SbF6)2 (reported earlier), the relative orientation of cluster pairs could be responsible for the formation of trans11. Diclusters of the type cis-[Re12Se16(PEt3)8L 2]4+ are required for potential thermolytic conversion to the cyclic tetracluster [Re24Se32(PEt3)16]8+. Factors relevant to the formation of this unknown cluster type are considered.

Original languageEnglish (US)
Pages (from-to)5173-5178
Number of pages6
JournalInorganic Chemistry
Volume36
Issue number23
StatePublished - 1997
Externally publishedYes

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Thermolysis
Condensation
condensation
Ligands
synthesis
Crystal structure
Stereochemistry
ligands
Substitution reactions
Nuclear magnetic resonance
Crystalline materials
X rays
crystal structure
stereochemistry
acetonitrile
pyridines
substitutes
nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{653c77e77833410a8761013d138ceaf4,
title = "Cluster Condensation by Thermolysis: Synthesis of a Rhomb-Linked Re12Se16 Dicluster and Factors Relevant to the Formation of the Re24Se32 Tetracluster",
abstract = "The cluster cis-[Re6Se8(PEt3)4I2] undergoes substitution reactions with neutral ligands L in the presence of AgSbF6 to afford the cis-disubstituted clusters [Re2Se8(PEt3)4L2] 2+(L = MeCN (6), t-BuCN, DMF, Me2SO (9)). Cluster 6 reacts with pyridine to give [Re6Se8(PEt3)4(py)2] 2+. Retention of stereochemistry was demonstrated from 31P NMR spectra and the crystal structure of [9](SbF6)2, which revealed the two Me2SO ligands to be O-bonded at adjacent Re sites of the face-capped octahedral [Re6(μ-Se)8]2+ core. The clusters cis-[Re6Se8(PEt3)4L 2]2+ are of interest as possible precursors to oligomeric clusters under thermolysis conditions where one or both ligands L are removed. Thermolysis of orange-red [6](SbF6)2 (180°C, 24 h) afforded a brown-green crystalline product identified by an X-ray structure determination to contain the dicluster [Re12Se16(PEt3)8(MeCN) 2]4+ (11). Two [Re6Se8]2+ cluster units are bridged by a Re2Se2 rhomb to afford the centrosymmetric core [Re12(μ3-Se)14(μ4Se) 2]4+, established recently for the dicluster [Re12Se16(PEt3)10]4+. The two acetonitrile ligands occur in a trans orientation on the two cluster units. From consideration of the crystal structure of the precursor compound [6](SbF6)2 (reported earlier), the relative orientation of cluster pairs could be responsible for the formation of trans11. Diclusters of the type cis-[Re12Se16(PEt3)8L 2]4+ are required for potential thermolytic conversion to the cyclic tetracluster [Re24Se32(PEt3)16]8+. Factors relevant to the formation of this unknown cluster type are considered.",
author = "Zhiping Zheng and Holm, {R. H.}",
year = "1997",
language = "English (US)",
volume = "36",
pages = "5173--5178",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

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TY - JOUR

T1 - Cluster Condensation by Thermolysis

T2 - Synthesis of a Rhomb-Linked Re12Se16 Dicluster and Factors Relevant to the Formation of the Re24Se32 Tetracluster

AU - Zheng, Zhiping

AU - Holm, R. H.

PY - 1997

Y1 - 1997

N2 - The cluster cis-[Re6Se8(PEt3)4I2] undergoes substitution reactions with neutral ligands L in the presence of AgSbF6 to afford the cis-disubstituted clusters [Re2Se8(PEt3)4L2] 2+(L = MeCN (6), t-BuCN, DMF, Me2SO (9)). Cluster 6 reacts with pyridine to give [Re6Se8(PEt3)4(py)2] 2+. Retention of stereochemistry was demonstrated from 31P NMR spectra and the crystal structure of [9](SbF6)2, which revealed the two Me2SO ligands to be O-bonded at adjacent Re sites of the face-capped octahedral [Re6(μ-Se)8]2+ core. The clusters cis-[Re6Se8(PEt3)4L 2]2+ are of interest as possible precursors to oligomeric clusters under thermolysis conditions where one or both ligands L are removed. Thermolysis of orange-red [6](SbF6)2 (180°C, 24 h) afforded a brown-green crystalline product identified by an X-ray structure determination to contain the dicluster [Re12Se16(PEt3)8(MeCN) 2]4+ (11). Two [Re6Se8]2+ cluster units are bridged by a Re2Se2 rhomb to afford the centrosymmetric core [Re12(μ3-Se)14(μ4Se) 2]4+, established recently for the dicluster [Re12Se16(PEt3)10]4+. The two acetonitrile ligands occur in a trans orientation on the two cluster units. From consideration of the crystal structure of the precursor compound [6](SbF6)2 (reported earlier), the relative orientation of cluster pairs could be responsible for the formation of trans11. Diclusters of the type cis-[Re12Se16(PEt3)8L 2]4+ are required for potential thermolytic conversion to the cyclic tetracluster [Re24Se32(PEt3)16]8+. Factors relevant to the formation of this unknown cluster type are considered.

AB - The cluster cis-[Re6Se8(PEt3)4I2] undergoes substitution reactions with neutral ligands L in the presence of AgSbF6 to afford the cis-disubstituted clusters [Re2Se8(PEt3)4L2] 2+(L = MeCN (6), t-BuCN, DMF, Me2SO (9)). Cluster 6 reacts with pyridine to give [Re6Se8(PEt3)4(py)2] 2+. Retention of stereochemistry was demonstrated from 31P NMR spectra and the crystal structure of [9](SbF6)2, which revealed the two Me2SO ligands to be O-bonded at adjacent Re sites of the face-capped octahedral [Re6(μ-Se)8]2+ core. The clusters cis-[Re6Se8(PEt3)4L 2]2+ are of interest as possible precursors to oligomeric clusters under thermolysis conditions where one or both ligands L are removed. Thermolysis of orange-red [6](SbF6)2 (180°C, 24 h) afforded a brown-green crystalline product identified by an X-ray structure determination to contain the dicluster [Re12Se16(PEt3)8(MeCN) 2]4+ (11). Two [Re6Se8]2+ cluster units are bridged by a Re2Se2 rhomb to afford the centrosymmetric core [Re12(μ3-Se)14(μ4Se) 2]4+, established recently for the dicluster [Re12Se16(PEt3)10]4+. The two acetonitrile ligands occur in a trans orientation on the two cluster units. From consideration of the crystal structure of the precursor compound [6](SbF6)2 (reported earlier), the relative orientation of cluster pairs could be responsible for the formation of trans11. Diclusters of the type cis-[Re12Se16(PEt3)8L 2]4+ are required for potential thermolytic conversion to the cyclic tetracluster [Re24Se32(PEt3)16]8+. Factors relevant to the formation of this unknown cluster type are considered.

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