Cage-fluorination during deboronation of meta-carboranes

被引:29
作者
Fox, MA [1 ]
Wade, K [1 ]
机构
[1] UNIV DURHAM,DEPT CHEM,DURHAM DH1 3LE,ENGLAND
关键词
carborane; deboronation; fluorination; fluoride ion; multinuclear NMR; rearrangement;
D O I
10.1016/S0277-5387(96)00520-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reactions of the meta carboranes 1,7-RR'-1,7-C2B10H10 (R, R' = Me; R = Ph, R' = Me; R, R' = Ph; R, R' = 4-FC6H4) with tetrabutylammonium fluoride hydrate (TBAFH) in refluxing tetrahydrofuran gave the corresponding nido-7,9-RR'-7,9-C2B9H10- salts, The aryl carboranes and TBAFH also yielded salts of the B-fluorinated anions 10-F-7,9-RR'-7,9-C2B9H9- and 3-F-7,9-RR'-7,9-C2B9H9-. The reaction of 1,7-(4-FC6H4)(2)-1,7-C2B10H10 with TBAFH monitored by F-19 NMR showed cage fluorination occurred during deboronation to give 10-F-7,9-(4-FC6H4)(2)-7,9-C2B9H9-. The latter anion rearranged spontaneously to 3-F-7,9-(4-FC6H4)(2)-7,9-C2B9H9- under the reaction conditions. The B-11, C-13, H-1 and F-19 NMR spectra of the carboranes have been assigned. (C) 1997 Published by Elsevier Science Ltd.
引用
收藏
页码:2517 / 2525
页数:9
相关论文
共 33 条
[11]   PREPARATION AND CHARACTERIZATION OF (3)-1,2- AND (3)-1,7-DICARBADODECAHYDROUNDECABORATE(-1) IONS [J].
HAWTHORNE, MF ;
YOUNG, DC ;
GARRETT, PM ;
OWEN, DA ;
SCHWERIN, SG ;
TEBBE, FN ;
WEGNER, PA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (04) :862-+
[12]   MODEL INTERMEDIATES FOR RHODACARBORANE CATALYSIS - ISOLATION OF A DISUBSTITUTED CLOSO-BIS(TRIPHENYLPHOSPHINE)HYDRIDORHODACARBORANE [J].
HEWES, JD ;
THOMPSON, M ;
HAWTHORNE, MF .
ORGANOMETALLICS, 1985, 4 (01) :13-17
[13]  
KNYAZEV SP, 1977, J GEN CHEM USSR, V47, P2627
[14]  
KNYAZEV SP, 1977, DOKLADY, V234, P323
[15]   SELECTIVE FLUORINATION OF ORTHO-CARBORANES AND META-CARBORANES - SYNTHESIS OF 9-MONOFLUORO-ORTHO-CARBORANE, 9,12-DIFLUORO-ORTHO-CARBORANE, 1,8,9,12-TRIFLUORO-ORTHO-CARBORANE, AND 8,9,10,12-TETRAFLUORO-ORTHO-CARBORANE AND 9-MONOFLUORO-META-CARBORANE, AND 9,10-DIFLUORO-META-CARBORANE - MOLECULAR-STRUCTURE OF 8,9,10,12-TETRAFLUORO-ORTHO-CARBORANE [J].
LEBEDEV, VN ;
BALAGUROVA, EV ;
POLYAKOV, AV ;
YANOVSKY, AI ;
STRUCHKOV, YT ;
ZAKHARKIN, LI .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1990, 385 (03) :307-318
[16]  
LEBEDEV VN, 1989, ORGANOMETAL CHEM USS, V2, P493
[17]   PREPARATION OF MONO(B-HYDROXY) DERIVATIVES OF 1,8-DIMETHYL-CLOSO-DICARBAUNDECABORANE(11) - THEIR PROPERTIES AND DERIVATIVE CHEMISTRY [J].
MERCER, GD ;
SCHOLER, FR .
INORGANIC CHEMISTRY, 1974, 13 (09) :2256-2260
[18]   PREPARATION OF 4-SUBSTITUTED (3)-1,7-DICARBA-NIDO-DODECAHYDROUNDECABORATE(-1) IONS AND 3-SUBSTITUTED 1,8-DICARBA-CLOSO-UNDECABORANE(11) [J].
OWEN, DA ;
HAWTHORN.MF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (22) :6002-&
[19]   DEGRADATIVE SUBSTITUTION OF 1,7-DIMETHYL-1,7-DICARBA-CLOSO-DODECABORANE TO FORM 3-ALKOXYNONAHYDRO-7,9-DIMETHYL-7,9-DICARBA-NIDO-UNDECABORATE(1-) IONS - ISOMERIC ANIONS [J].
PRETZER, WR ;
THOMPSON, DA ;
RUDOLPH, RW .
INORGANIC CHEMISTRY, 1975, 14 (10) :2571-2572
[20]  
STANKO VI, 1967, J GEN CHEM USSR, V37, P486