SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE OSMIUM CLUSTER DIANIONS [OS17(CO)36]2- AND [OS20(CO)40]2-

被引:25
作者
GADE, LH
JOHNSON, BFG
LEWIS, J
MCPARTLIN, M
POWELL, HR
RAITHBY, PR
WONG, WT
机构
[1] UNIV EDINBURGH,DEPT CHEM,KINGS BLDG,W MAINS RD,EDINBURGH EH9 3JJ,MIDLOTHIAN,SCOTLAND
[2] UNIV CAMBRIDGE,CHEM LAB,CAMBRIDGE CB2 1EW,ENGLAND
[3] UNIV N LONDON,SCH CHEM,LONDON N7 8DB,ENGLAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1994年 / 04期
关键词
D O I
10.1039/dt9940000521
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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-degrees-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 [PBu(n)4]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.
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页码:521 / 532
页数:12
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共 52 条
  • [21] ERTL G, 1979, GAZZ CHIM ITAL, V109, P217
  • [22] Fantucci P., 1988, Elemental and Molecular Clusters. Proceedings of the 13th International School, P125
  • [23] MIXED PLATINUM RHODIUM CARBONYL CLUSTERS - THE ISOLATION OF [PT4RH18(CO)35]4-, AN EXAMPLE OF A CHERRY-LIKE CLUSTER WITH A SEMIEXPOSED TETRAPLATINUM CORE
    FUMAGALLI, A
    MARTINENGO, S
    CIANI, G
    MASCIOCCHI, N
    SIRONI, A
    [J]. INORGANIC CHEMISTRY, 1992, 31 (02) : 336 - 340
  • [24] PHOTOCHEMICAL CORE MANIPULATION IN HIGH-NUCLEARITY OS-HG CLUSTERS
    GADE, LH
    JOHNSON, BFG
    LEWIS, J
    MCPARTLIN, M
    KOTCH, T
    LEES, AJ
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (23) : 8698 - 8704
  • [25] DYNAMIC BEHAVIOR OF HIGH-NUCLEARITY OSMIUM MERCURY CLUSTERS IN SOLUTION
    GADE, LH
    JOHNSON, BFG
    LEWIS, J
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (05): : 933 - 937
  • [26] THE SYNTHESIS OF THE CLUSTER DIANION [OS10C(CO)24]2- BY PYROLYSIS - X-RAY STRUCTURE-ANALYSIS OF [N(PPH3)2]2[OS10C(CO)24] AND [OS5C(CO)14H(NC5H4)]
    JACKSON, PF
    JOHNSON, BFG
    LEWIS, J
    NELSON, WJH
    MCPARTLIN, M
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1982, (10): : 2099 - 2107
  • [27] SYNTHESIS OF THE CARBIDO CLUSTER [OS10(CO)24C]2- AND THE X-RAY STRUCTURE OF [OS10(CO)24C][(PH3P)2N]2
    JACKSON, PF
    JOHNSON, BFG
    LEWIS, J
    MCPARTLIN, M
    NELSON, WJH
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1980, (05) : 224 - 226
  • [28] THE PREPARATION, CHARACTERIZATION, AND SOME REACTIONS OF [OS3(CO)11(NCME)]
    JOHNSON, BFG
    LEWIS, J
    PIPPARD, DA
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1981, (02): : 407 - 412
  • [29] ELECTRONIC SHELL STRUCTURE AND ABUNDANCES OF SODIUM CLUSTERS
    KNIGHT, WD
    CLEMENGER, K
    DEHEER, WA
    SAUNDERS, WA
    CHOU, MY
    COHEN, ML
    [J]. PHYSICAL REVIEW LETTERS, 1984, 52 (24) : 2141 - 2143
  • [30] A METHOD OF ABSORPTION CORRECTION BY X-RAY INTENSITY MEASUREMENTS
    KOPFMANN, G
    HUBER, R
    [J]. ACTA CRYSTALLOGRAPHICA SECTION A-CRYSTAL PHYSICS DIFFRACTION THEORETICAL AND GENERAL CRYSTALLOGRAPHY, 1968, A 24 : 348 - &