New directions of cluster chemistry - The story of the [Re 63-Se)8]2+ clusters

Hugh D. Selby, Zhiping Zheng

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Transition metal clusters are a unique class of chemical substances. Not only do they have well-defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal-metal bonded species. In this Comment our recent results in developing synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability are summarized. Specifically, we have explored the uses of site-differentiated cluster complexes, featuring the [Re63-Se) 8]2+ core, as stereospecific building blocks for supramolecular construction. A great variety of cluster-supported molecular and supramolecular architectures have been realized, some of which display rather interesting electronic and spectroscopic properties. Following a distinctly different line of research, we have also pursued the activation of nitriles toward nucleophilic attack, as a result of their prior coordination to the Lewis acidic rhenium sites of the cluster. The isolation and characterization of imino ester complexes proved that the cluster core acts as a powerful Lewis acid catalyst. Subsequent photocleavage in the presence of nitriles, regenerating the procatalytic solvate, marks the completion of one cycle of a potentially photocatalytic process. It is not unreasonable to imagine applying cluster-based Lewis acid activation to a range of substrates beyond nitriles and alcohols. The work therefore marks the beginning of what promises to be an exciting new chapter in cluster chemistry.

Original languageEnglish (US)
Pages (from-to)75-102
Number of pages28
JournalComments on Inorganic Chemistry
Volume26
Issue number1-2
DOIs
StatePublished - 2005

Fingerprint

Nitriles
Lewis Acids
Metals
Chemical activation
Rhenium
Molecular structure
Transition metals
Esters
Alcohols
Catalysts
Substrates
Direction compound

Keywords

  • Catalysis
  • Crystal engineering
  • Metal clusters
  • Site-differentiation
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

New directions of cluster chemistry - The story of the [Re 63-Se)8]2+ clusters. / Selby, Hugh D.; Zheng, Zhiping.

In: Comments on Inorganic Chemistry, Vol. 26, No. 1-2, 2005, p. 75-102.

Research output: Contribution to journalArticle

@article{b88866381477475aa004777823cfccc4,
title = "New directions of cluster chemistry - The story of the [Re 6(μ3-Se)8]2+ clusters",
abstract = "Transition metal clusters are a unique class of chemical substances. Not only do they have well-defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal-metal bonded species. In this Comment our recent results in developing synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability are summarized. Specifically, we have explored the uses of site-differentiated cluster complexes, featuring the [Re6(μ3-Se) 8]2+ core, as stereospecific building blocks for supramolecular construction. A great variety of cluster-supported molecular and supramolecular architectures have been realized, some of which display rather interesting electronic and spectroscopic properties. Following a distinctly different line of research, we have also pursued the activation of nitriles toward nucleophilic attack, as a result of their prior coordination to the Lewis acidic rhenium sites of the cluster. The isolation and characterization of imino ester complexes proved that the cluster core acts as a powerful Lewis acid catalyst. Subsequent photocleavage in the presence of nitriles, regenerating the procatalytic solvate, marks the completion of one cycle of a potentially photocatalytic process. It is not unreasonable to imagine applying cluster-based Lewis acid activation to a range of substrates beyond nitriles and alcohols. The work therefore marks the beginning of what promises to be an exciting new chapter in cluster chemistry.",
keywords = "Catalysis, Crystal engineering, Metal clusters, Site-differentiation, Supramolecular chemistry",
author = "Selby, {Hugh D.} and Zhiping Zheng",
year = "2005",
doi = "10.1080/02603590590920569",
language = "English (US)",
volume = "26",
pages = "75--102",
journal = "Comments on Inorganic Chemistry",
issn = "0260-3594",
publisher = "Taylor and Francis Ltd.",
number = "1-2",

}

TY - JOUR

T1 - New directions of cluster chemistry - The story of the [Re 6(μ3-Se)8]2+ clusters

AU - Selby, Hugh D.

AU - Zheng, Zhiping

PY - 2005

Y1 - 2005

N2 - Transition metal clusters are a unique class of chemical substances. Not only do they have well-defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal-metal bonded species. In this Comment our recent results in developing synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability are summarized. Specifically, we have explored the uses of site-differentiated cluster complexes, featuring the [Re6(μ3-Se) 8]2+ core, as stereospecific building blocks for supramolecular construction. A great variety of cluster-supported molecular and supramolecular architectures have been realized, some of which display rather interesting electronic and spectroscopic properties. Following a distinctly different line of research, we have also pursued the activation of nitriles toward nucleophilic attack, as a result of their prior coordination to the Lewis acidic rhenium sites of the cluster. The isolation and characterization of imino ester complexes proved that the cluster core acts as a powerful Lewis acid catalyst. Subsequent photocleavage in the presence of nitriles, regenerating the procatalytic solvate, marks the completion of one cycle of a potentially photocatalytic process. It is not unreasonable to imagine applying cluster-based Lewis acid activation to a range of substrates beyond nitriles and alcohols. The work therefore marks the beginning of what promises to be an exciting new chapter in cluster chemistry.

AB - Transition metal clusters are a unique class of chemical substances. Not only do they have well-defined molecular structures, they also exhibit interesting and potentially useful properties that are inherent to metal-metal bonded species. In this Comment our recent results in developing synthetic methodologies necessary to bring a cluster system out of the limited sphere of fundamental cluster chemistry and into general synthetic applicability are summarized. Specifically, we have explored the uses of site-differentiated cluster complexes, featuring the [Re6(μ3-Se) 8]2+ core, as stereospecific building blocks for supramolecular construction. A great variety of cluster-supported molecular and supramolecular architectures have been realized, some of which display rather interesting electronic and spectroscopic properties. Following a distinctly different line of research, we have also pursued the activation of nitriles toward nucleophilic attack, as a result of their prior coordination to the Lewis acidic rhenium sites of the cluster. The isolation and characterization of imino ester complexes proved that the cluster core acts as a powerful Lewis acid catalyst. Subsequent photocleavage in the presence of nitriles, regenerating the procatalytic solvate, marks the completion of one cycle of a potentially photocatalytic process. It is not unreasonable to imagine applying cluster-based Lewis acid activation to a range of substrates beyond nitriles and alcohols. The work therefore marks the beginning of what promises to be an exciting new chapter in cluster chemistry.

KW - Catalysis

KW - Crystal engineering

KW - Metal clusters

KW - Site-differentiation

KW - Supramolecular chemistry

UR - http://www.scopus.com/inward/record.url?scp=21044432056&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=21044432056&partnerID=8YFLogxK

U2 - 10.1080/02603590590920569

DO - 10.1080/02603590590920569

M3 - Article

VL - 26

SP - 75

EP - 102

JO - Comments on Inorganic Chemistry

JF - Comments on Inorganic Chemistry

SN - 0260-3594

IS - 1-2

ER -