Metal-Rich Oxametallaboranes of Group 5 Metals: Synthesis and Structure of a Face-Fused μ7-Boride Cluster

被引:11
作者
Prakash, Rini [1 ]
De, Anangsha [1 ]
Kirubakaran, Bakthavachalam [1 ]
Ghosh, Sundargopal [1 ]
机构
[1] Indian Inst Technol Madras, Dept Chem, Madras 600036, Tamil Nadu, India
关键词
POLYHEDRAL AZAMETALLABORANE CHEMISTRY; HYPOELECTRONIC METALLABORANES; ELECTRONIC-STRUCTURES; CARBONYL-COMPOUNDS; BORIDE CLUSTERS; OXABORANE ANION; CP-ASTERISK; BORON ATOM; MONOBORANE; COMPLEXES;
D O I
10.1021/acs.inorgchem.8b02512
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Aerobic oxidation of metallaborane compounds is an unexplored field apart from the few reports on accidental oxidation leading to oxametallaboranes. An effective method for the synthesis of group 5 oxametallaboranes has been developed by the oxidation of [(Cp*M)(2)(B2H6)(2)] (M = Ta/Nb) (Cp* = eta(5)-C5Me5). The reaction of [(Cp*M)(2)(B2H6)(2)] (M = Ta/Nb) with 02 gas at room temperature yielded oxametallaboranes [(Cp*M)(2)(B4H10O)] (for 1, M = Nb; for 2, M = Ta). Density functional theory calculations signify an increase in the HOMO LUMO energy gap for 1 and 2 as compared to that for the parent metallaboranes, [(Cp*M)(2)(B2H6)(2)] (M = Ta/Nb). Reaction of 1 and 2 with [Ru-3(CO)(12)] led to the isolation of fused metallaborane clusters [(Cp*Nb)(2)(B2H40){Ru(CO)(2)}(2)(B2H4){Ru(CPO)(3)}(2){mu-H}(4)] (3) and [(Cp*Ta)(2)(B3H4O){Ru(CO)(2)}(3){mu(7)-B}{mu-CO}(2){y-H-4}4] (4). The structure of 3 may be considered as a fusion of five subunits [two tetrahedra (Td), two square pyramids (sqp), and one trigonal bipyramid (tbp)]. One of the key features of cluster 4 is the presence of a mu(7)-boride atom that shares three cluster units (one monocapped trigonal prism and two Td). All the compounds have been characterized by mass spectrometry, infrared spectroscopy, and H-1, C-13, and B-11 nuclear magnetic resonance spectroscopy, and the structural types were unequivocally established by crystallographic analysis of compounds 1, 3, and 4.
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页码:14748 / 14757
页数:10
相关论文
共 93 条
  • [41] Expansion of iridaborane clusters by addition of monoborane. Novel metallaboranes and mechanistic detail
    Ghosh, Sundargopal
    Noll, Bruce C.
    Fehlner, Thomas P.
    [J]. DALTON TRANSACTIONS, 2008, (03) : 371 - 378
  • [42] SOME THOUGHT-PROVOKING POLYHEDRAL BORANE CHEMISTRY
    GREENWOOD, NN
    KENNEDY, JD
    [J]. PURE AND APPLIED CHEMISTRY, 1991, 63 (03) : 317 - 326
  • [43] Grimes R.N., 1982, METAL INTERACTIONS B
  • [44] AZARHODA-CLOSO-DODECABORANE
    HANSEN, HP
    MULLER, J
    ENGLERT, U
    PAETZOLD, P
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (10): : 1377 - 1379
  • [45] A METAL ENCAPSULATED BORON ATOM - PREPARATION AND STRUCTURE OF [FE4(CO)12B(AUPPH3)3]
    HARPP, KS
    HOUSECROFT, CE
    RHEINGOLD, AL
    SHONGWE, MS
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (14) : 965 - 966
  • [46] MOLECULAR-STRUCTURE OF 1-AZA-CLOSO-DODECABORANE(12) - EXPERIMENTAL AND THEORETICAL REFINEMENT
    HNYK, D
    BUHL, M
    SCHLEYER, PV
    VOLDEN, HV
    GUNDERSEN, S
    MULLER, J
    PAETZOLD, P
    [J]. INORGANIC CHEMISTRY, 1993, 32 (11) : 2442 - 2445
  • [47] Housecroft C. E, 1990, BORANES METALLOBORAN
  • [48] FROM METALLABORANES TO TRANSITION-METAL BORIDES - THE CHEMISTRY OF METAL-RICH METALLABORANE CLUSTERS
    HOUSECROFT, CE
    [J]. POLYHEDRON, 1987, 6 (11) : 1935 - 1958
  • [49] TRANSITION-METAL BORIDE CLUSTERS AT THE MOLECULAR-LEVEL
    HOUSECROFT, CE
    [J]. COORDINATION CHEMISTRY REVIEWS, 1995, 143 : 297 - 330
  • [50] MACROPOLYHEDRAL BORON-CONTAINING CLUSTER CHEMISTRY - THE ISOLATION AND CHARACTERIZATION OF THE 18-VERTEX AZABORANE ANTI-[9-NB17H20]
    JELINEK, T
    KENNEDY, JD
    STIBR, B
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (06) : 677 - 678