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
[1]  
BRATTSEV VA, 1975, J GEN CHEM USSR, V45, P1173
[2]   REACTIONS INVOLVING UNDECAHYDRO-7,9-DICARBA-NIDO-UNDECABORATE(2-) ION, 7,9-B9C2H112- - INSERTION, OXIDATIVE CLOSURE, AND ADDITION [J].
CHOWDHRY, V ;
PRETZER, WR ;
RAI, DN ;
RUDOLPH, RW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (14) :4560-4565
[3]   C-ARYLATION AND C-HETEROARYLATION OF ICOSAHEDRAL CARBORANES VIA THEIR COPPER(I) DERIVATIVES [J].
COULT, R ;
FOX, MA ;
GILL, WR ;
HERBERTSON, PL ;
MACBRIDE, JAH ;
WADE, K .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1993, 462 (1-2) :19-29
[4]   STRUCTURES OF [HNET3]+ AND [ME3NCH2C6H5]+ SALTS OF [7,8-PH2-7,8-NIDO-C2B9H10]- [J].
COWIE, J ;
DONOHOE, DJ ;
DOUEK, NL ;
WELCH, AJ .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1993, 49 :710-714
[5]   CARBORANES .1. PREPARATION AND CHEMISTRY OF 1-ISOPROPENYLCARBORANE AND ITS DERIVATIVES (A NEW FAMILY OF STABLE CLOVOBORANES) [J].
FEIN, MM ;
COHEN, MS ;
MAYES, N ;
SCHWARTZ, N ;
BOBINSKI, J .
INORGANIC CHEMISTRY, 1963, 2 (06) :1111-&
[6]   Fluoride-ion deboronation of p-fluorophenyl-ortho- and -meta-carboranes. NMR evidence for the new fluoroborate, HOBHF2- [J].
Fox, MA ;
MacBride, JAH ;
Wade, K .
POLYHEDRON, 1997, 16 (14) :2499-2507
[7]   Deboronation of C-substituted ortho- and meta-closo-carboranes using ''wet'' fluoride ion solutions [J].
Fox, MA ;
Gill, WR ;
Herbertson, PL ;
MacBride, JAH ;
Wade, K ;
Colquhoun, HM .
POLYHEDRON, 1996, 15 (04) :565-571
[8]   OXIDATION OF (3)-1,7-DICARBA-NIDO-DODECAHYDROUNDECABORATE(-1) ION . A NEW PREPARATION OF 1,3-DICARBA-NIDO-NONABORANE(13) [J].
GARRETT, PM ;
GEORGE, TA ;
HAWTHORN.MF .
INORGANIC CHEMISTRY, 1969, 8 (09) :2008-&
[9]   THERMAL ISOMERIZATION OF C-PHENYLDICARBAUNDECABORATE(12) [J].
GARRETT, PM ;
TEBBE, FN ;
HAWTHORNE, MF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (22) :5016-&
[10]   SYNTHESIS OF NOVEL SUBSTITUTED (3)-1,7-DICARBAUNDECABORATE(12) IONS FROM 1,8-DICARBA-CLOSO-UNDECABORANE(11) AND CARBANIONS [J].
HAWTHORN.MF ;
OWEN, DA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (21) :5912-&