SYNTHESIS AND MOLECULAR-STRUCTURES OF THE BASE-STABILIZED ARYLBORON DICHLORIDES BCL2(2,6-(NET2CH2)(2)C6H3) AND BCL2(2-(NME2CH2)C6H4)

The reaction of Li{2,6-(NEt2CH2)(2)C6H3} with BCl3 . Et2O in hexane yi elds BCl2[2-{BCl3 (NEt2CH2):}-6-(NEt2CH2)C6H3] (1) as the thermodynami cally favoured product. If BCl3, pyridine is employed, only Cl{2,6-(NE t2CH2)(2)C6H3}(2) is formed. 1 reacts with [PPh4]Cl to give the BC3-fr ee product BCl2{2,6-(NEt2CH2)(2)C6H3} (2) with formation of [PPh4][BCl 4]. Li{2-(NMe2CH2)C6H4} reacts with BCl3, to give BCl2{2-(NMe2CH2)C6H4 ) (3). 1-3 were characterized spectroscopically (NMR, IR, MS) and thei r crystal structures were determined: 1, T = 260(2) K, triclinic, P (1 ) over bar, with a = 7.069(2) Angstrom, b, = 10.837(5) Angstrom, c = 1 4.090(5) Angstrom, alpha = 90.09(2)degrees, beta = 104.16(2)degrees, g amma = 97.35(2)degrees, V = 1037.3(7) Angstrom(3), Z = 2, d(calcd) = 1 .429 g cm(-3) 3409 independent reflections, and R1 = 0.0460, omega R2 = 0.0889 (for reflections with I>2 sigma(I)), R1 = 0.0752, omega R2 = 0.1082 (all data); 2, T = 213(2) K, monoclinic, P2(1)/c, with a = 13.1 797(9) Angstrom, b = 7.5833(5) Angstrom, c=18.6796(13) Angstrom,beta=1 08.974(1) V=1765.5(2) Angstrom(3), Z=4, d(calcd) = 1.238 g cm(-3), 317 4 independent reflections, and 1;1 = 0.0334, omega R2 = 0.0824 (for re flections with I > 2 sigma(I)), R1 = 0.0436, omega R2 = 0.0874 (all da ta); 3, T = 213(2) K, orthorhombic, P2(1)2(1)2(1), with a = 9.4540(8)A ngstrom, b = 9.5650(8) Angstrom, c = 11.6900(10) Angstrom, V = 1057.1( 2) Angstrom(3), Z = 4, d(calcd)= 1.357 g cm(-3), 1913 independent refl ections, and R1 = 0.0298, omega R2 = 0.0651 (for reflections with I >2 sigma(I), R1 = 0.0334, omega R2 = 0.0673 (all data).