Gas-phase lithium-cation basicities of some benzene derivatives -: An experimental and theoretical study

被引:42
作者
Gal, JF
Maria, PC
Decouzon, M
Mó, O
Yáñez, M
机构
[1] Univ Nice, F-06108 Nice 2, France
[2] Univ Autonoma Madrid, Dept Quim, E-28049 Madrid, Spain
关键词
Li+ basicities; benzene derivatives; density functional theory calculations; FT-ICR;
D O I
10.1016/S1387-3806(02)00699-1
中图分类号
O64 [物理化学(理论化学)、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号
070203 ; 070304 ; 081704 ; 1406 ;
摘要
The gas-phase lithium-cation basicities of a series of monosubstituted benzene derivatives, namely C6H5X (X=H, Me, CH=CH2, OH, OMe, SH, Cl, Br) have been measured by means of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The structures of the corresponding complexes and their relative stabilities were investigated with B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) density functional theory calculations. In all cases, the pi-complexes are favored with respect to those in which the metal monocation interacts with the substituent. These latter kind of complexes, which are entropically favored with respect to the pi-complexes, are found to be chelated species, in which Li+ bridges the heteroatom of the substituent and the ipso carbon atom. The Li+ basicity of the benzene derivatives investigated reflects the electron-donor ability of the aromatic moiety as a function of the substituent. Consistently, there is a linear correlation between the Li+ basicity and the frequency of the vertical displacement of Li+ with respect to the aromatic ring.
引用
收藏
页码:445 / 456
页数:12
相关论文
共 48 条
[1]   The P4••• Li+ ion in the gas phase:: A planetary system [J].
Abboud, JLM ;
Alkorta, I ;
Dávalos, JZ ;
Gal, JF ;
Herreros, M ;
Maria, PC ;
Mó, O ;
Molina, MT ;
Notario, R ;
Yáñez, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (18) :4451-4454
[2]  
ABBOUD JLM, 1992, NEW J CHEM, V16, P739
[3]   EXPERIMENTAL AND THEORETICAL-STUDY OF LI+ AFFINITIES OF METHYLDIAZOLES [J].
ALCAMI, M ;
MO, O ;
YANEZ, M ;
ANVIA, F ;
TAFT, RW .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (12) :4796-4804
[4]   A MOLECULAR-ORBITAL STUDY OF AZOLE-LI+ COMPLEXES [J].
ALCAMI, M ;
MO, O ;
YANEZ, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (10) :3929-3936
[5]   ENHANCED LI+ BINDING-ENERGIES OF SOME AZINES - A MOLECULAR-ORBITAL STUDY [J].
ALCAMI, M ;
MO, O ;
DEPAZ, JJG ;
YANEZ, M .
THEORETICA CHIMICA ACTA, 1990, 77 (01) :1-15
[6]  
ALCAMI M, 1996, MOL ELECTROSTATIC PO, P407
[7]   Absolute binding energies of alkali-metal cation complexes with benzene determined by threshold collision-induced dissociation experiments and ab initio theory [J].
Amicangelo, JC ;
Armentrout, PB .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (48) :11420-11432
[8]   FORMATION OF 3-MEMBERED AND 4-MEMBERED-RING STRUCTURES FOR THE LI+ ADDUCTS OF APPROPRIATE AZINES [J].
ANVIA, F ;
WALSH, S ;
CAPON, M ;
KOPPEL, IA ;
TAFT, RW ;
DEPAZ, JLG ;
CATALAN, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (13) :5095-5097
[9]  
Armentrout P. B., 1996, Organometallic Ion Chemistry
[10]   A COMPARISON OF THE ACCURACY OF DIFFERENT FUNCTIONALS [J].
BAUSCHLICHER, CW .
CHEMICAL PHYSICS LETTERS, 1995, 246 (1-2) :40-44