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

doi:10.1021/ic970727x

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 [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.

Original language	English (US)
Pages (from-to)	5173-5178
Number of pages	6
Journal	Inorganic Chemistry
Volume	36
Issue number	23
DOIs	https://doi.org/10.1021/ic970727x
State	Published - 1997
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@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",

doi = "10.1021/ic970727x",

language = "English (US)",

volume = "36",

pages = "5173--5178",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "23",

}

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

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