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Fine Tuning of Metallaborane Geometries: Chemistry of Metallaboranes of Early Transition Metals Derived from Metal Halides and Monoborane Reagents

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Title Fine Tuning of Metallaborane Geometries: Chemistry of Metallaboranes of Early Transition Metals Derived from Metal Halides and Monoborane Reagents
 
Creator BOSE, SK
GEETHARANI, K
RAMKUMAR, V
MOBIN, SM
GHOSH, S
 
Subject cp-asterisk
structural-characterization
electronic-structures
molecular-structures
crystal-structures
complexes
clusters
reactivity
tetrahydroborate
eta(5)-c5me5
cluster compounds
metallaboranes
niobium
tantalum
vanadium
 
Description Reaction of [Cp(n)MCl(4-x)] (M=V: n=x=2; M=Nb: n=1, x=0) or [Cp*TaCl(4)] (CP=eta(5)-C(5)H(5), Cp*=eta(5)-C(5)Me(5)), with [LiBH(4)center dot thf] at -70 degrees C followed by thermolysis at 85 degrees C in the presence of [BH(3)center dot thf] yielded the hydrogen-rich metallaboranes [(CpM)(2)-(B(2)H(6))(2)] (1: M=V; 2: M=Nb) and [(Cp*Ta)(2)(B(2)H(6))(2)] (3) in modest to high yields. Complexes 1 and 3 are the first structurally characterized compounds with a metal-metal bond bridged by two hexahydroborate (B(2)H(6)) groups forming a symmetrical complex. Addition of [BH(3)center dot thf] to 3 results in formation of a metallaborane [(Cp*Ta)(2)B(4)H(8)(mu-BH(4))] (4) containing a tetrahydroborate ligand, [BH(4)](-), bound exo to the bicapped tetrahedral cage [(Cp*Ta)(2)B(4)H(8)] by two Ta-H-B bridge bonds. The interesting structural feature of 4 is the coordination of the bridging tetrahydroborate group, which has two B-H bonds coordinated to the tantalum atoms. All these new metallaboranes have been characterized by mass, (1)H, (11)B, and (13)C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of 1-4.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2011-09-01T16:27:59Z
2011-12-26T12:59:43Z
2011-12-27T05:52:27Z
2011-09-01T16:27:59Z
2011-12-26T12:59:43Z
2011-12-27T05:52:27Z
2009
 
Type Article
 
Identifier CHEMISTRY-A EUROPEAN JOURNAL, 15(48), 13483-13490
0947-6539
http://dx.doi.org/10.1002/chem.20090181.9
http://dspace.library.iitb.ac.in/xmlui/handle/10054/12821
http://hdl.handle.net/10054/12821
 
Language en