Zirconium tetrachloride-formaldehyde σ-complexes:: A computational and spectroscopic investigation

被引:7
作者
Bernardi, N [1 ]
Bottoni, A [1 ]
Casolari, S [1 ]
Tagliavini, E [1 ]
机构
[1] Univ Bologna, Dipartimento Chim G Ciamician, I-40126 Bologna, Italy
关键词
D O I
10.1021/jo990876s
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
We have carried out a combined theoretical-experimental study of the structures and energies of ZrCl4-aldehyde complexes using C-13 NMR spectroscopy and a DFT (B3LYP) computational approach. The computational investigation has demonstrated the existence of different types of complexes: a 1:1 complex (H2CO-ZrCl4), various 2:1 complexes ((H2CO)(2)-ZrCl4), and several dimeric species. The analysis of the energies involved in the formation of the various complexes has indicated that the dimeric species should correspond to the only adduct observed in the C-13 NMR spectra (carbonyl resonance at 226.96 ppm) when a 1:1 ZrCl4/aldehyde molar ratio is used, while the 2:1 complex should be responsible for the signal at 224.30 ppm that is recorded when this molar ratio is 1:2.
引用
收藏
页码:4783 / 4790
页数:8
相关论文
共 41 条
[1]   LEWIS-ACID CATALYZED TRANS-HYDROSTANNYLATION OF ACETYLENES [J].
ASAO, N ;
LIU, JX ;
SUDOH, T ;
YAMAMOTO, Y .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (23) :2405-2406
[2]   Lewis acid-catalyzed hydrostannation of acetylenes. Regio- and stereoselective trans-addition of tributyltin hydride and dibutyltin dihydride [J].
Asao, N ;
Liu, JX ;
Sudoh, T ;
Yamamoto, Y .
JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (14) :4568-4571
[3]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[4]   A DFT investigation of ethylene dimerization catalyzed by Ni(0) complexes [J].
Bernardi, F ;
Bottoni, A ;
Rossi, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (31) :7770-7775
[5]  
BODESCHI P, 1995, TETRAHEDRON LETT, V36, P787
[6]   THE ROLE OF TRANSITION-METAL ATOMS AS HYDROGEN-BOND ACCEPTORS - A NEUTRON-DIFFRACTION STUDY OF [NPRN4]2[PTCL4].CIS-[PTCL2(NH2ME)2] AT 20-K [J].
BRAMMER, L ;
CHARNOCK, JM ;
GOGGIN, PL ;
GOODFELLOW, RJ ;
ORPEN, AG ;
KOETZLE, TF .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (07) :1789-1798
[7]   COMPLEXES BETWEEN FORMALDEHYDE AND TITANIUM TETRACHLORIDE - AN ABINITIO STUDY [J].
BRANCHADELL, V ;
OLIVA, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (11) :4357-4364
[8]   COMPLEXES BETWEEN FORMALDEHYDE AND BORON TRIHALIDES - AN ABINITIO STUDY [J].
BRANCHADELL, V ;
OLIVA, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (11) :4132-4136
[9]   Chiral-achiral ligand synergy: activation of a zirconium-BINOL Lewis acid complex by the addition of 4-tert-butylcalix[4]arene [J].
Casolari, S ;
Cozzi, PG ;
Orioli, P ;
Tagliavini, E ;
UmaniRonchi, A .
CHEMICAL COMMUNICATIONS, 1997, (21) :2123-2124
[10]   CATALYTIC ASYMMETRIC-SYNTHESIS OF HOMOALLYLIC ALCOHOLS [J].
COSTA, AL ;
PIAZZA, MG ;
TAGLIAVINI, E ;
TROMBINI, C ;
UMANIRONCHI, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (15) :7001-7002