Halogenation of (CF<sub>3</sub>)<sub>3</sub>B·NH<sub>3</sub>: <i>N</i>,<i>N</i>-Dihaloamino- and Halo-tris(trifluoromethyl)borates [(CF<sub>3</sub>)<sub>3</sub>B−NX<sub>2</sub>]<sup>-</sup> and [(CF<sub>3</sub>)<sub>3</sub>B−X]<sup>-</sup>, X = F, Cl, Br
作者:David J. Brauer、Hans Bürger、Yonas Chebude、Gottfried Pawelke
DOI:10.1021/ic990352a
日期:1999.9.1
(CF3)(3)B . NH3 (1) reacts with cesium hypochlorite or hypobromite to form the respective N,N-dichloroamina- or N,N-dibromoamino-tris(trifluoromethyl)borates Cs[(CF3)(3)B-NCl2] (2) or Cs[(CF3)(3)B-NBr2] (3). Fluorination of 2 or 3 in CH3CN yields Cs[(CF3)(3)B-NF2] (4) and Cs[(CF3)(3)B-F] (5). The fluorination reactions produce numerous byproducts; one of these, Cs[(CF3)(3)B-NH-COCBr3] (6), has been isolated from the reaction of 3. Compound 5 was also formed when 2 or 3 was treated with AgF2. Pyrolysis of 2 at 190 degrees C and 3 at 140 degrees C. yielded the haloborates Cs[(CF3)(3)B-Cl] (7) and Cs[(CF3)(3)B-Br] (8), respectively. The constitution of the novel berates has been deduced from multinuclear NMR, IR, Raman, and mass spectra. The structures of 6, 7, 8, and Cs[(CF3)(3)B-NH2 x (CF3)(3)B -NH3] (1a) have been investigated by single-crystal X-ray diffraction. 1a: C6H5B2CSF18N2, monoclinic, C2/c, a = 22.802(5) Angstrom, b = 7.0965(13) Angstrom, c = 11.000(2) Angstrom, beta = 102.79(2)degrees, Z = 4, R1 = 0.0374, wR2 = 0.0945. 6: C5HBBr3CsF9NO, monoclinic, C2/c, a = 20.121(4) Angstrom, b = 16.765(3) Angstrom, c = 10.005(2) Angstrom, beta = 118.416(12)degrees, Z = 8 R1 = 0.0680, wR2 = 0.1766. 7: C3BClCsF9, cubic, P2(1)3, a = 9.8059(9) Angstrom, Z = 4, R1 = 0.0252, wR2 = 0.0639, 8: C3BBrCsF9, cubic, P2(1)3, a = 9.9001(14) Angstrom, Z = 4, R1 = 0.0631, wR2 = 0.1490.
(CF3)3B·NH3(1)与铯次氯酸盐或次溴酸盐反应,生成相应的N,N-二氯氨基或N,N-二溴氨基三(三氟甲基)硼酸铯Cs[(CF3)3B-NCl2](2)或Cs[(CF3)3B-NBr2](3)。在CH3CN中对2或3进行氟化,得到Cs[(CF3)3B-NF2](4)和Cs[(CF3)3B-F](5)。氟化反应产生大量副产物;其中之一,Cs[(CF3)3B-NH-COCBr3](6),已从3的反应中分离出来。当2或3与AgF2处理时,也会形成5。在190°C下对2进行热解,在140°C下对3进行热解,分别生成卤化硼Cs[(CF3)3B-Cl](7)和Cs[(CF3)3B-Br](8)。新型硼酸盐的结构已通过多核NMR、红外、拉曼和质谱分析得出。6、7、8以及Cs[(CF3)3B-NH2 x (CF3)3B-NH3](1a)的结构已在单晶X射线衍射中进行了研究。
1a:C6H5B2CSF18N2,单斜晶系,C2/c,a = 22.802(5)Å,b = 7.0965(13)Å,c = 11.000(2)Å,β = 102.79(2)°,Z = 4,R1 = 0.0374,wR2 = 0.0945。
6:C5HBBr3CsF9NO,单斜晶系,C2/c,a = 20.121(4)Å,b = 16.765(3)Å,c = 10.005(2)Å,β = 118.416(12)°,Z = 8,R1 = 0.0680,wR2 = 0.1766。
7:C3BClCsF9,立方晶系,P2(1)3,a = 9.8059(9)Å,Z = 4,R1 = 0.0252,wR2 = 0.0639。
8:C3BBrCsF9,立方晶系,P2(1)3,a = 9.9001(14)Å,Z = 4,R1 = 0.0631,wR2 = 0.1490。