The Relation Between Polyhedral Borane Sandwiches and Endohedral Complexes; the Electronic Structure and Stability of X@YmBnHn+mq (X = He, Ne, Li, Be; Y = B, C, Si; m = 0-3; n = 12-9; q = -2 to +2), (C2B4H6)2Xq (X = Li, Al, Si; q = -3, -1, 0) and X2@B17H17q (X = He, Li; q = -2, 0)

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Title:The Relation Between Polyhedral Borane Sandwiches and Endohedral Complexes; the Electronic Structure and Stability of X@YmBnHn+mq (X = He, Ne, Li, Be; Y = B, C, Si; m = 0-3; n = 12-9; q = -2 to +2), (C2B4H6)2Xq (X = Li, Al, Si; q = -3, -1, 0) and X2@B17H17q (X = He, Li; q = -2, 0)
Creators:
Jemmis, Eluvathingal D.
Jayasree, Elambalassery G.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 7, pp. 965-990
Uncontrolled Keywords:Sandwich complexes, <i>Ab initio</i> calculations, Endohedral complexes, Polyhedral boranes, Carboranes, Metallaboranes

Abstract

An electronic structural connection is established for sandwich complexes and polyhedral boranes containing encapsulated atoms. The charge requirements of these extreme geometrical patterns, examples <strong>3</strong> and <strong>9</strong>, depend on the size of the central atom or on the distance between the adjacent rings. While going from the endohedral to the corresponding sandwich complexes the unoccupied a<sub>2u</sub> and e<sub>g</sub> molecular orbitals are stabilized considerably requiring additional 6 electrons for stability. The two endohedral atoms in the doped structures <strong>10</strong> resulting from the multidecker sandwich complexes <strong>4</strong> are found to stabilize the large borane skeleton. The energetics and geometries of the relatively less explored endohedral boranes show that endohedral silaboranes are more stable than the endohedral carbaboranes. In general, when an atom is encapsulated in a borane cage, its skeletal bonds are elongated. The exo bonds are shortened due to the possible reduction in the torsional strain between the adjacent vertices. A comparison of the endohedral complexes with the corresponding exo isomers shows that encapsulation makes the system more strained. <p>

Title:The Relation Between Polyhedral Borane Sandwiches and Endohedral Complexes; the Electronic Structure and Stability of X@YmBnHn+mq (X = He, Ne, Li, Be; Y = B, C, Si; m = 0-3; n = 12-9; q = -2 to +2), (C2B4H6)2Xq (X = Li, Al, Si; q = -3, -1, 0) and X2@B17H17q (X = He, Li; q = -2, 0)
Creators:
Jemmis, Eluvathingal D.
Jayasree, Elambalassery G.
Uncontrolled Keywords:Sandwich complexes, <i>Ab initio</i> calculations, Endohedral complexes, Polyhedral boranes, Carboranes, Metallaboranes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:7
Page Range:pp. 965-990
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20020965UNSPECIFIED
ID Code:1967
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Jemmis, Eluvathingal D.; Jayasree, Elambalassery G. (2002) The Relation Between Polyhedral Borane Sandwiches and Endohedral Complexes; the Electronic Structure and Stability of X@YmBnHn+mq (X = He, Ne, Li, Be; Y = B, C, Si; m = 0-3; n = 12-9; q = -2 to +2), (C2B4H6)2Xq (X = Li, Al, Si; q = -3, -1, 0) and X2@B17H17q (X = He, Li; q = -2, 0). Collection of Czechoslovak Chemical Communications, 67 (7). pp. 965-990. ISSN 0010-0765

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