KINETICS AND MECHANISM OF NUCLEOPHILIC SUBSTITUTION IN OCTAHEDRAL METAL COMPLEXES .1. KINETICS OF SOLVATION OF, AND SUBSTITUTION OF PYRIDINE BY CHLORIDE ION IN, BISPYRIDINE TETRACHLORO TIN(4) COMPLEX IN NITROBENZENE

被引:10
作者
SANDHU, SS
BHATIA, JC
机构
[1] Department of Chemistry, Punjabi University, Patiala
来源
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY | 1969年 / 31卷 / 08期
关键词
D O I
10.1016/0022-1902(69)80577-4
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A solution of bispyridine tetrachloro tin (IV) in nitrobenzene shows an increase in conductance with time which suggests solvation of the complex. In the presence of the nucleophilic reagents, HCl, SOCl2, C6H5COCl and CH3COCl, there is a greater increase in conductance and nucleophilic substitution of pyridine by chloride ion. The data for rate constant ks, for solvation, and stepwise constants, k1 and k2, for nucleophilic substitution by chloride ions, which have been obtained conductometrically at three different temperatures in the range 30-45°, are in favour of first order reactions. The rate constants indicate that solvation is much slower than substitution by chloride ion, k1 or k2 ≫ ks and k2/k1 ≈ 2-3. Arrhenius parameters and other relevant functions have been calculated. The values of frequency factor and significantly positive entropy of activation suggest the substitution to proceed through an SNI mechanism. © 1969.
引用
收藏
页码:2445 / &
相关论文
共 22 条
[1]  
BEATTIE IR, 1961, J CHEM SOC, P2585
[2]  
BEATTIS, 1962, CHEM IND, P1429
[3]  
CLARK HC, 1963, P CHEM SOC LONDON, P85
[4]  
Guggenheim EA, 1926, PHILOS MAG, V2, P538
[5]   Derivates of hexachloro-tin acid [J].
Gutbier, A ;
Kunze, G ;
Guhring, E .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1923, 128 (02) :169-178
[6]  
LEWIS, 1960, MODERN COORDINATI ED, P97
[7]  
MANHAS BS, 1964, THESIS U TEXAS
[8]  
MORGAN GT, 1924, J CHEM SOC, P372
[9]   ACETYL CHLORIDE AS A POLAR SOLVENT .1. SOLUBILITY OF SUBSTANCES AND FORMATION OF SOLVATES IN ACETYL CHLORIDE [J].
PAUL, RC ;
SINGH, D ;
SANDHU, SS .
JOURNAL OF THE CHEMICAL SOCIETY, 1959, (JAN) :315-319
[10]  
PAUL RC, 1958, J INDIAN CHEM SOC, V35, P489