Synthesis and structural characterisation of the osmium cluster dianions [Os17(CO)36]2- and [Os20(CO)40]2-

Lutz H. Gade; Brian F.G. Johnson; Jack Lewis; Mary McPartlin; Harold R. Powell; Paul R. Raithby; Wing Tak Wong

doi:10.1039/DT9940000521

Synthesis and structural characterisation of the osmium cluster dianions [Os₁₇(CO)₃₆]^2- and [Os₂₀(CO)₄₀]^2-

Lutz H. Gade, Brian F.G. Johnson, Jack Lewis, Mary McPartlin, Harold R. Powell, Paul R. Raithby, Wing Tak Wong

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

Abstract

The cluster dianions [Os₁₇(CO)₃₆]^2- and [Os₂₀(CO)₄₀]^2-, the largest osmium carbonyl clusters isolated to date, have been obtained by vacuum pyrolysis of [Os₃(CO)₁₀(NCMe)₂] at temperatures above 260°C and initial pressures of ca. 10^-3 Torr. A single-crystal X-ray structure analysis of [AsPh₄]₂[Os₁₇(CO)₃₆] has established a trigonal-bipyramidal core of 14 osmium atoms which is capped by three additional Os atoms. Carbon-13 NMR studies indicate a high degree of fluxionality in the cluster. The crystal structure analysis of [PBuⁿ₄]₂[Os₂₀(CO)₄₀] has revealed a tetrahedral cubic close-packed metal core of twenty osmium atoms which represents the first example of a totally symmetrical array of metal atoms of this nuclearity, a geometrical arrangement previously proposed for both bare and ligated eicosanuclear metal clusters. The structure of the latter bears close resemblance to the chemisorption of CO on metal (111) surfaces at high density. An interpretation of some aspects of its redox chemical behaviour on the basis of the electronic structure of the compound is given.

Original language	English
Pages (from-to)	521-532
Number of pages	12
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	4
DOIs	https://doi.org/10.1039/DT9940000521
Publication status	Published - 1994

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1039/DT9940000521

Cite this

@article{8adb4f66d7e54f318ce576eca0759a61,

title = "Synthesis and structural characterisation of the osmium cluster dianions [Os17(CO)36]2- and [Os20(CO)40]2-",

abstract = "The cluster dianions [Os17(CO)36]2- and [Os20(CO)40]2-, the largest osmium carbonyl clusters isolated to date, have been obtained by vacuum pyrolysis of [Os3(CO)10(NCMe)2] at temperatures above 260°C and initial pressures of ca. 10-3 Torr. A single-crystal X-ray structure analysis of [AsPh4]2[Os17(CO)36] has established a trigonal-bipyramidal core of 14 osmium atoms which is capped by three additional Os atoms. Carbon-13 NMR studies indicate a high degree of fluxionality in the cluster. The crystal structure analysis of [PBun4]2[Os20(CO)40] has revealed a tetrahedral cubic close-packed metal core of twenty osmium atoms which represents the first example of a totally symmetrical array of metal atoms of this nuclearity, a geometrical arrangement previously proposed for both bare and ligated eicosanuclear metal clusters. The structure of the latter bears close resemblance to the chemisorption of CO on metal (111) surfaces at high density. An interpretation of some aspects of its redox chemical behaviour on the basis of the electronic structure of the compound is given.",

author = "Gade, {Lutz H.} and Johnson, {Brian F.G.} and Jack Lewis and Mary McPartlin and Powell, {Harold R.} and Raithby, {Paul R.} and Wong, {Wing Tak}",

year = "1994",

doi = "10.1039/DT9940000521",

language = "English",

pages = "521--532",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "4",

}

TY - JOUR

T1 - Synthesis and structural characterisation of the osmium cluster dianions [Os17(CO)36]2- and [Os20(CO)40]2-

AU - Gade, Lutz H.

AU - Johnson, Brian F.G.

AU - Lewis, Jack

AU - McPartlin, Mary

AU - Powell, Harold R.

AU - Raithby, Paul R.

AU - Wong, Wing Tak

PY - 1994

Y1 - 1994

N2 - The cluster dianions [Os17(CO)36]2- and [Os20(CO)40]2-, the largest osmium carbonyl clusters isolated to date, have been obtained by vacuum pyrolysis of [Os3(CO)10(NCMe)2] at temperatures above 260°C and initial pressures of ca. 10-3 Torr. A single-crystal X-ray structure analysis of [AsPh4]2[Os17(CO)36] has established a trigonal-bipyramidal core of 14 osmium atoms which is capped by three additional Os atoms. Carbon-13 NMR studies indicate a high degree of fluxionality in the cluster. The crystal structure analysis of [PBun4]2[Os20(CO)40] has revealed a tetrahedral cubic close-packed metal core of twenty osmium atoms which represents the first example of a totally symmetrical array of metal atoms of this nuclearity, a geometrical arrangement previously proposed for both bare and ligated eicosanuclear metal clusters. The structure of the latter bears close resemblance to the chemisorption of CO on metal (111) surfaces at high density. An interpretation of some aspects of its redox chemical behaviour on the basis of the electronic structure of the compound is given.

AB - The cluster dianions [Os17(CO)36]2- and [Os20(CO)40]2-, the largest osmium carbonyl clusters isolated to date, have been obtained by vacuum pyrolysis of [Os3(CO)10(NCMe)2] at temperatures above 260°C and initial pressures of ca. 10-3 Torr. A single-crystal X-ray structure analysis of [AsPh4]2[Os17(CO)36] has established a trigonal-bipyramidal core of 14 osmium atoms which is capped by three additional Os atoms. Carbon-13 NMR studies indicate a high degree of fluxionality in the cluster. The crystal structure analysis of [PBun4]2[Os20(CO)40] has revealed a tetrahedral cubic close-packed metal core of twenty osmium atoms which represents the first example of a totally symmetrical array of metal atoms of this nuclearity, a geometrical arrangement previously proposed for both bare and ligated eicosanuclear metal clusters. The structure of the latter bears close resemblance to the chemisorption of CO on metal (111) surfaces at high density. An interpretation of some aspects of its redox chemical behaviour on the basis of the electronic structure of the compound is given.

UR - http://www.scopus.com/inward/record.url?scp=37049081823&partnerID=8YFLogxK

U2 - 10.1039/DT9940000521

DO - 10.1039/DT9940000521

M3 - Article

AN - SCOPUS:37049081823

SN - 1472-7773

SP - 521

EP - 532

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 4

ER -

Synthesis and structural characterisation of the osmium cluster dianions [Os₁₇(CO)₃₆]^2- and [Os₂₀(CO)₄₀]^2-

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this