C-C bond variation in the 1-phenyl-o-carborane:: Steric versus electronic effects

被引：56

作者：

Glukhov, IV ^{[1
]}

Antipin, MY ^{[1
]}

Lyssenko, KA ^{[1
]}

机构：

[1] Russian Acad Sci, AN Nesmeyanov Organoelement Cpds Inst, Moscow 119991, Russia

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2004年 / 07期

关键词：

ab initio calculations; atoms in molecules theory; C-C bond elongation; carboranes; electron density; hydrogen bonds;

D O I：

10.1002/ejic.200300743

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Using the "Atoms in molecules" topological theory the nature of the C-carb-C-carb bond variation in 1-phenyl-o-carborane upon rotation of the phenyl ring was investigated within B3LYP/6-31G * * calculations. Despite the low barrier to the rotation of the phenyl ring, the bond paths linking hydrogen atoms of the phenyl ring and the ones of the carborane cage were found for all conformations. The length of the C-carb-C-carb bond increases by 0.031 Angstrom without large energetic inputs due to back-donation of the pi-density of the phenyl ring to the antibonding C-carb-C-carb orbital. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

引用

页码：1379 / 1384

页数：6

共 39 条

[1]

ALEKSEYEVA ES, 1998, COMMUNICATION

[2] Supramolecular assemblies of globular main group cage species [J].

Andrews, PC ;

Hardie, MJ ;

Raston, CL .

COORDINATION CHEMISTRY REVIEWS, 1999, 189 :169-198

[3] Molecular crystal structure and electron density distribution in the crystal of pentaethyl-1,5-dicarba-closo-pentaborane [C2B3(Et)(5)] at 120 K [J].

Antipin, M ;

Boese, R ;

Blaser, D ;

Maulitz, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (02) :326-333

[4] PROPERTIES OF ATOMS IN MOLECULES - STRUCTURES AND REACTIVITIES OF BORANES AND CARBORANES [J].

BADER, RFW ;

LEGARE, DA .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1992, 70 (02) :657-676

[5] A bond path: A universal indicator of bonded interactions [J].

Bader, RFW .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (37) :7314-7323

[6]

BONE RGA, 1994, CHEM PHYS LETT, V228, P160

[7] Synthesis and characterisation of pseudocloso iridium and ruthenium diphenyl carbaboranes. Molecular structures of 1,2-Ph(2)-3-(eta-C6H6)-3,1,2-pseudocloso-RuC2B9H9 and 1,2-Ph(2)-3-(cym)-3,1,2-pseudocloso-RuC2B9H9 (cym equals p-cymene) and individual gauge for localised orbitals calculations on carbametallaboranes [J].

Brain, PT ;

Buhl, M ;

Cowie, J ;

Lewis, ZG ;

Welch, AJ .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (02) :231-237

[8] 1-Phenyl-1,2-dicarba-closo-dodecaborane, 1-Ph-1,2-closo-C2B10H11. Synthesis, characterization, and structure as determined in the gas phase by electron diffraction, in the crystalline phase at 199 K by X-ray diffraction, and by ab initio computations [J].

Brain, PT ;

Cowie, J ;

Donohoe, DJ ;

Hnyk, D ;

Rankin, DWH ;

Reed, D ;

Reid, BD ;

Robertson, HE ;

Welch, AJ ;

Hofmann, M ;

Schleyer, PV .

INORGANIC CHEMISTRY, 1996, 35 (06) :1701-1708

[9] CLOSO TO HYPER-CLOSO TRANSFORMATIONS IN A TUNGSTACARBORANE CAGE SYSTEM - CRYSTAL-STRUCTURE OF [NET4][W2(MU-CC6H4ME-4)(CO)2(ETA-5-7,8-ME2-7,8-C2B9H9)(ETA-6-7,8-ME2-7,8-C2B9H8-10-(CH2C6H4ME-4))] [J].

CARR, N ;

MULLICA, DF ;

SAPPENFIELD, EL ;

STONE, FGA .

ORGANOMETALLICS, 1992, 11 (11) :3697-3704

[10] 1,2,4-Triazinylcarboranes:: a new approach to the synthesis and the crystal structures of 1-(3,6-ditolyl-1,2,4-triazin-5-yl)-2-phenyl-1,2-dicarba-closo-dodecaborane and 1,7-bis[6-phenyl-3-(4-chlorophenyl)-1,2,4-triazin-5-yl]-1,7-dicarba-closo-dodecaborane [J].

Chupakhin, ON ;

Prokhorov, AM ;

Kozhevnikov, DN ;

Rusinov, VL ;

Kalinin, VN ;

Olshevskaya, VA ;

Glukhov, IV ;

Antipin, MY .

MENDELEEV COMMUNICATIONS, 2003, (04) :165-167

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