SYNTHESIS AND PROPERTIES OF COORDINATION-COMPLEXES OF ACRYLONITRILE, METHACRYLONITRILE AND CIS TRANS-CROTONONITRILE WITH THE CHLORIDES BCL3, TICL4, SNCL4 AND SBCL5

被引:6
作者
ELERIAN, MAI [1 ]
HUGGETT, PG [1 ]
WADE, K [1 ]
JENNINGS, JR [1 ]
机构
[1] ICI PLC,DEPT RES & TECHNOL,MIDDLESBROUGH TS6 8JE,CLEVELAND,ENGLAND
关键词
D O I
10.1016/S0277-5387(00)86132-X
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The coordination complexes of acrylonitrile, CH2 = CHCN, methacrylonitrile, CH2 = CMeCN, and cis/trans crotononitrile, MeCH = CHCN, with a series of metal and metalloid chlorides, MCln, where M = Ti(IV), Sn(IV), B(III) and Sb(V), have been prepared and the coordination is shown to be sigma-bonded through the nitrogen "lone pair" to the metal centre. The olefinic protons of the 1:1 complexes of TiCl4 and SnCl4, on coordination, show an upfield shift in the H-1 NMR spectra. Electrical conductivity measurements in nitrobenzene solution show all the addition compounds of SnCl4 and TiCl4 to be non-electrolytes and therefore non-ionic. Consistent with this observation, all of the compounds except for the SbCl5 complex are volatile at room temperature while the 2:1 complexes of TiCl4 with acrylonitrile and methacrylonitrile tend to dissociate in the vapour phase into the 1:1 complex and free ligand. The IR spectra of the complexes have also been studied and in all cases the cyanide stretching frequency increases, showing coordination occurs through the nitrile group.
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页码:2131 / 2136
页数:6
相关论文
共 18 条
[1]   THE ACCEPTOR PROPERTIES OF QUADRIPOSITIVE SILICON, GERMANIUM, TIN, AND LEAD [J].
BEATTIE, IR .
QUARTERLY REVIEWS, 1963, 17 (04) :382-405
[2]   VIBRATIONAL SPECTRA AND NORMAL MODES OF VIBRATION OF 2-CYANOPROPENE AND 2-CYANOPROPENE-D5 [J].
BRAGIN, J ;
KIZER, KL ;
DURIG, JR .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1971, 38 (02) :289-&
[3]   THE COORDINATION CHEMISTRY OF ACRYLONITRILE [J].
BRYAN, SJ ;
HUGGETT, PG ;
WADE, K ;
DANIELS, JA ;
JENNINGS, JR .
COORDINATION CHEMISTRY REVIEWS, 1982, 44 (02) :149-189
[4]   RELATIVE LEWIS ACIDITIES OF SILICON TETRACHLORIDE, GERMANIUM TETRACHLORIDE AND TIN TETRACHLORIDE TOWARDS ACRYLONITRILE - VAPOR PRESSURE-COMPOSITION STUDIES [J].
DANIELS, JA ;
JENNINGS, JR ;
HUGGETT, PG ;
WADE, K .
INORGANIC & NUCLEAR CHEMISTRY LETTERS, 1978, 14 (11) :445-449
[5]   VIBRATIONAL SPECTRA OF TRANS-CROTONONITRILE AND CIS-CROTONONITRILE [J].
DURIG, JR ;
TONG, CK ;
HAWLEY, CW ;
BRAGIN, J .
JOURNAL OF PHYSICAL CHEMISTRY, 1971, 75 (01) :44-&
[8]   THE VIBRATIONAL SPECTRUM AND THERMODYNAMIC FUNCTIONS OF ACRYLONITRILE [J].
HALVERSON, F ;
STAMM, RF ;
WHALEN, JJ .
JOURNAL OF CHEMICAL PHYSICS, 1948, 16 (08) :808-816
[9]  
HERBERHOLD M, 1972, METAL COMPLEXES 1, V2, P290
[10]   THE RELATIVE LEWIS ACIDITIES OF SILICON TETRACHLORIDE, GERMANIUM TETRACHLORIDE AND TIN TETRACHLORIDE TOWARDS ACETONITRILE, ACRYLONITRILE, ETHYL-ACETATE, DIETHYL-ETHER AND TETRAHYDROFURAN - VAPOR PRESSURE-COMPOSITION STUDIES [J].
HUGGETT, PG ;
MANNING, K ;
WADE, K .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1980, 42 (05) :665-673