13 顶点碳硼烷 μ-1,2-(CH2)4-1,2-C2B11H11 与亲核试剂的反应：对产物形成的键合效应。

Reaction of 13-vertex carborane μ-1,2-(CH2)4-1,2-C2B11H11 with nucleophiles: linkage effect on product formation.

机构信息

Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong , Shatin, New Territories, Hong Kong, China.

出版信息

Inorg Chem. 2013 Sep 16;52(18):10677-84. doi: 10.1021/ic401744h. Epub 2013 Aug 26.

DOI:10.1021/ic401744h

PMID:23978282

Abstract

The length of C,C'-linkage has a great influence on the reactivity of 13-vertex carboranes. Reaction of 1,2-(CH2)4-1,2-C2B11H11 (1a) with Et2NH gave a 1:1 adduct nido-7-NEt2H-μ-1,3-(CH2)4-1,3-C2B11H11 (2). Compound 1a reacted with Me2NLi or Et2NLi to afford nido-9-Nu-μ-7,8,10-(CH2)4CCH-B11H10 (Nu = NMe2, 3; Nu = NEt2, 4). Complex 4 was also obtained by deprotonation of 2. Treatment of 1a with MeOH/base generated nido-3-OMe-μ-1,2-(CH2)4-1,2-C2B11H11 (5) at room temperature, which was converted to nido-μ-7,8-(CH2)4CHB(OMe)2-7-CB10H11 (6) upon heating in the presence of Et3N. Complex 6 was oxidized by H2O2 to the corresponding alcohol μ-7,8-(CH2)4CHOH-7-CB10H11 (7) or hydrolyzed to the boronic acid μ-7,8-(CH2)4CHB(OH)2-7-CB10H11 (8). Reaction of 1a with (4-MeC6H4)SNa produced a CB11(-) anion closo-μ-1,2-(CH2)4CHS(4-MeC6H4)-1-CB11H10 (9). The above complexes were fully characterized by (1)H, (13)C, and (11)B NMR spectroscopic data and elemental analyses. Molecular structures of 1-7 and 9 were further confirmed by single-crystal X-ray analyses.

摘要

C,C'- 键的长度对 13 顶点碳硼烷的反应性有很大影响。1,2-(CH2)4-1,2-C2B11H11（1a）与 Et2NH 反应得到 1:1 加合物 nido-7-NEt2H-μ-1,3-(CH2)4-1,3-C2B11H11（2）。化合物 1a 与 Me2NLi 或 Et2NLi 反应生成 nido-9-Nu-μ-7,8,10-(CH2)4CCH-B11H10（Nu = NMe2，3；Nu = NEt2，4）。4 也可以通过 2 的脱质子化得到。用 MeOH/碱处理 1a 在室温下生成 nido-3-OMe-μ-1,2-(CH2)4-1,2-C2B11H11（5），当存在 Et3N 时，在加热条件下转化为 nido-μ-7,8-(CH2)4CHB(OMe)2-7-CB10H11（6）。复合物6 被 H2O2 氧化为相应的醇μ-7,8-(CH2)4CHOH-7-CB10H11（7）或水解为硼酸μ-7,8-(CH2)4CHB(OH)2-7-CB10H11（8）。1a 与(4-MeC6H4)SNa 反应生成 CB11(-) 阴离子 closo-μ-1,2-(CH2)4CHS(4-MeC6H4)-1-CB11H10（9）。这些配合物均通过 1H、13C 和 11B NMR 光谱数据和元素分析进行了充分表征。1-7 和9 的分子结构通过单晶 X 射线分析进一步得到证实。