Structural characterization of tris(pyrazolyl)hydroborato and tris(2-pyridylthio)methyl lithium compounds: Lithium in uncommon trigonal pyramidal and trigonal monopyramidal coordination environments

被引:18
作者
Chakrabarti, Neena [1 ]
Sattler, Wesley [1 ]
Parkin, Gerard [1 ]
机构
[1] Columbia Univ, Dept Chem, New York, NY 10027 USA
基金
美国国家科学基金会;
关键词
Tris(pyrazolyl)hydroborato; Tris(2-pyridylthio)methyl; Lithium; Trigonal pyramidal; Trigonal monopyramidal; LIGAND-EXCHANGE PROCESSES; EFFECTIVE CORE POTENTIALS; X-RAY STRUCTURES; AB-INITIO; MOLECULAR CALCULATIONS; MAGNETIC-RESONANCE; SYNTHETIC ANALOGS; CHEMICAL-SHIFTS; TRIS(PYRAZOLYL)BORATE LIGANDS; COPPER(I) COMPLEXES;
D O I
10.1016/j.poly.2013.02.008
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
X-ray diffraction reveals that the molecular structures of the tris(pyrazolyl)hydroborato and tris(2-pyridylthio)methyl lithium compounds, [Tp(But,R)]Li (R = H, Me) and [kappa(4)-Tptm]Li, respectively exhibit three-coordinate trigonal pyramidal and four-coordinate trigonal monopyramidal coordination geometries, both of which are uncommon for lithium. Accordingly, [Tp(But)]Li and [Tp(But,Me)]Li bind additional ligands to form four-coordinate adducts, such as [Tp(But)]Li(NCMe), [Tp(But,Me)]Li(NCMe), [Tp(But)]Li(pz(But)H), [Tp(But,Me)]Li(pz(But)H)center dot(pz(But)H), [Tp(But,Me)]Li(OH2), [Tp(')(But)(Me)]Li(OH2)center dot(pzH) and [Tp(But)]Li(OH2)center dot(THF), each of which has been structurally characterized by X-ray diffraction in the solid state. In solution, however, dissociation of the ligand (L) from the adducts [Tp(But,R)]Li is facile such that the adducts exist in equilibrium with [Tp(')(But)(R)]Li and L, as demonstrated by NMR spectroscopic studies. (C) 2013 Elsevier Ltd. All rights reserved.
引用
收藏
页码:235 / 246
页数:12
相关论文
共 121 条
[11]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[12]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[13]   From simple rings to one-dimensional channels with calix[8]arenes, water clusters, and alkali metal ions [J].
Bergougnant, Remi D. ;
Robin, Adeline Y. ;
Fromm, Katharina M. .
TETRAHEDRON, 2007, 63 (44) :10751-10757
[14]   Systematic structural coordination chemistry of p-tert-butyltetrathiacalix[4]arene:: 1.: Group 1 elements and congeners [J].
Bilyk, A ;
Hall, AK ;
Harrowfield, JM ;
Hosseini, MW ;
Skelton, BW ;
White, AH .
INORGANIC CHEMISTRY, 2001, 40 (04) :672-686
[15]   Trapping of n-butyllithium dimer by a trilithiated derivative of {Al[N(H)But]3}2 [J].
Brask, JK ;
Chivers, T ;
Yap, GPA .
CHEMICAL COMMUNICATIONS, 1998, (22) :2543-2544
[16]   TRIS(TRIMETHYLSILYLAMINO)SILANES RSI(NHSIME3)3 - SYNTHESIS, CRYSTAL AND MOLECULAR-STRUCTURE OF 3 DIMERIC TRILITHIO DERIVATIVES [J].
BRAUER, DJ ;
BURGER, H ;
LIEWALD, GR ;
WILKE, J .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1985, 287 (03) :305-320
[17]   Transition metals as Lewis bases: "Z-type" boron ligands and metal-to-boron dative bonding [J].
Braunschweig, Holger ;
Dewhurst, Rian D. .
DALTON TRANSACTIONS, 2011, 40 (03) :549-558
[18]   Diaquobis-μ-dimethylsulfoxo)bis(dimethylsulfoxo)dilithium tetraphenylborate [J].
Butler, JM ;
Gray, GM .
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY, 2003, 33 (07) :557-562
[19]   Diaquo(1,2-dimethoxyethane)lithium tetraphenylborate [J].
Butler, JM ;
Gray, GM .
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY, 2002, 32 (07) :171-175
[20]   Syntheses and structures of lithium and sodium salt complexes with alkylpolyamine ligands [J].
Buttery, Jarrod H. N. ;
Plackett, Neil C. ;
Skelton, Brian W. ;
Whitaker, Claire R. ;
White, Allan H. .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2006, 632 (10-11) :1856-1869