Crystal structure of a heavier alkali metal diisopropylamide complex:: a discrete (KN)2 ring dimer with TMEDA chelation and short intramolecular K•••H(C)contacts

被引:23
作者
Clegg, W
Kleditzsch, S
Mulvey, RE
O'Shaughnessy, P
机构
[1] Univ Newcastle Upon Tyne, Dept Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England
[2] Univ Strathclyde, Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland
基金
英国工程与自然科学研究理事会;
关键词
amide; crystal structure; intramolecular bonding; potassium;
D O I
10.1016/S0022-328X(98)00391-X
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Synthesized by treating diisopropylamine with a potassium reagent (the solid isolated from a 1:1 reaction mixture of potassium t-butoxide and n-butyllithium) in the presence of N,N,N',N'-tetramethylenediamine (TMEDA), the potassium diisopropylamide complex [((Pr2NK)-Pr-i. TMEDA)(2)] has been subjected to a low temperature X-ray diffraction study. This reveals a discrete dimeric arrangement centred on an asymmetrical (KN)(2) cyclic ring, with bond lengths of 2.706(2) and 2.837(2) Angstrom and endocyclic bond angles of 100.54(5) and 79.46(5)degrees (at K and N, respectively). Terminal, chelating TMEDA ligands complete the distorted tetrahedral N, primary coordination sphere about the K+ cations. However, there are several secondary intramolecular K ... H(C) contacts involving methyl fragments of the diisopropylamido ligands. (C) 1998 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:193 / 196
页数:4
相关论文
共 16 条
[1]   X-ray crystallographic studies and comparative reactivity studies of a sodium diisopropylamide (NDA) complex and related hindered amides [J].
Andrews, PC ;
Barnett, NDR ;
Mulvey, RE ;
Clegg, W ;
ONeil, PA ;
Barr, D ;
Cowton, L ;
Dawson, AJ ;
Wakefield, BJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 518 (1-2) :85-95
[2]   ISOSTRUCTURAL POTASSIUM AND SODIUM DI-NITROGEN FUNCTIONALIZED AMIDES - SYNTHESES AND CRYSTAL-STRUCTURES OF [PH(2-PYR)NK.TMEDA]2 AND [ME(2-PYR)NNA.TMEDA]2 [J].
ANDREWS, PC ;
BAKER, DR ;
MULVEY, RE ;
CLEGG, W ;
ONEIL, PA .
POLYHEDRON, 1991, 10 (15) :1839-1841
[3]   CRYSTAL-STRUCTURE OF LITHIUM DIISOPROPYLAMIDE (LDA) - AN INFINITE HELICAL ARRANGEMENT COMPOSED OF NEAR-LINEAR N-LI-N UNITS WITH 4 UNITS PER TURN OF HELIX [J].
BARNETT, NDR ;
MULVEY, RE ;
CLEGG, W ;
ONEIL, PA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :8187-8188
[4]   STRUCTURE AND REACTIVITY OF LITHIUM DIISOPROPYLAMIDE IN THE PRESENCE OF N,N,N',N'-TETRAMETHYLETHYLENEDIAMINE [J].
BERNSTEIN, MP ;
ROMESBERG, FE ;
FULLER, DJ ;
HARRISON, AT ;
COLLUM, DB ;
LIU, QY ;
WILLIARD, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (13) :5100-5110
[5]   CARBON-HYDROGEN-TRANSITION METAL BONDS [J].
BROOKHART, M ;
GREEN, MLH .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 250 (01) :395-408
[6]   Tris(trimethylsilyl)silanides of the heavier alkali metals - A structural study [J].
Klinkhammer, KW .
CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (09) :1418-1431
[7]   CRYSTAL HANDLING AT LOW-TEMPERATURES [J].
KOTTKE, T ;
STALKE, D .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1993, 26 :615-619
[8]  
LOCHMANN L, 1996, TETRAHEDRON LETT, P257
[9]   SODIUM AND POTASSIUM FLUOROSILYLAMIDES - SYNTHESIS AND CRYSTAL-STRUCTURES [J].
PIEPER, U ;
STALKE, D ;
VOLLBRECHT, S ;
KLINGEBIEL, U .
CHEMISCHE BERICHTE, 1990, 123 (05) :1039-1041
[10]  
SHELDRICK GM, 1995, SHELXTL MANUAL VERSI