Large-bite diboranes for the μ(1,2) complexation of hydrazine and cyanide.
Large-bite diboranes for the μ(1,2) complexation of hydrazine and cyanide.
复制标题
DOI：
10.1039/c8sc01877d
复制
发表时间：
2018-08-07
期刊：
影响因子：
8.4
通讯作者：
Gabbaï FP
中科院分区：
文献类型：
--
作者：
Chen CH;Gabbaï FP
基于1，8-联苯二基骨架的乙硼烷显示出对肼的高亲和力，同时也表现为氰化物海绵。作为我们对多齿刘易斯酸作为双原子分子的主体的化学的兴趣的一部分，我们研究了具有大的硼-硼分离的双齿硼烷的合成和配位化学。本文报道了一种新的二硼烷化合物1，8-双（二均三甲苯基硼基）三蝶烯（2）的合成，并与最近报道的1，8-双（二均三甲苯基硼基）联苯（1）的性质进行了比较。这些比较研究表明，这两种乙硼烷具有一些重要的差异。如循环伏安法所示，1比2更缺电子;它也采用了更紧凑和刚性的结构，硼-硼分离（4.566（5）Ω）比2（5.559（4）Ω）短2.1 Ω。这些差异似乎决定了这两种化合物的配位行为。当2对肼保持惰性时，我们观察到1形成非常稳定的μ（1，2）肼络合物，其也可以通过将1的溶液与稀肼水溶液分层时的相转移获得。该络合物的稳定性进一步反映在其在室温下不与苯甲醛反应。我们还研究了1和2对阴离子的行为。在甲醇/三氯甲烷（1/1vol）中，两种化合物都能选择性地与氰化物结合，形成以B-CN-B桥为核心的μ（1，2）螯合物。在质子介质中的竞争实验表明，由1形成的阴离子氰化物络合物是最稳定的，即使在（C6 F5）3B的存在下也没有解络合的证据。
A diborane based on the 1,8-biphenylenediyl backbone displays a high affinity for hydrazine while also behaving as a cyanide sponge. As part of our interest in the chemistry of polydentate Lewis acids as hosts for diatomic molecules, we have investigated the synthesis and coordination chemistry of bidentate boranes that feature a large boron–boron separation. In this paper, we describe the synthesis of a new example of such a diborane, namely 1,8-bis(dimesitylboryl)triptycene (2) and compare its properties to those of the recently reported 1,8-bis(dimesitylboryl)biphenylene (1). These comparative studies reveal that these two diboranes feature some important differences. As indicated by cyclic voltammetry, 1 is more electron deficient than 2; it also adopts a more compact and rigid structure with a boron–boron separation (4.566(5) Å) shorter by ∼1 Å than that in 2 (5.559(4) Å). These differences appear to dictate the coordination behaviour of these two compounds. While 2 remains inert toward hydrazine, we observed that 1 forms a very stable μ(1,2) hydrazine complex which can also be obtained by phase transfer upon layering a solution of 1 with a dilute aqueous hydrazine solution. The stability of this complex is further reflected by its lack of reaction with benzaldehyde at room temperature. We have also investigated the behaviour of 1 and 2 toward anions. In MeOH/CHCl3 (1/1 vol) both compounds selectively bind cyanide to form the corresponding μ(1,2) chelate complexes with a B–CN–B bridge at their cores. Competition experiments in protic media show that the anionic cyanide complex formed by 1 is the most stable, with no evidence of decomplexation even in the presence of (C6F5)3B.
登录
查看更多内容
影响因子：
4
作者：
Chiu, Ching-Wen;Gabbaie, Francois P.
通讯作者：
Gabbaie, Francois P.
影响因子：
15
作者：
Brunkan, NM;Brestensky, DM;Jones, WD
通讯作者：
Jones, WD
影响因子：
16.6
作者：
Emslie, DJH;Piers, WE;Parvez, M
通讯作者：
Parvez, M
影响因子：
4.3
作者：
Chen, Pangkuan;Marshall, Ariel S.;Jaekle, Frieder
通讯作者：
Jaekle, Frieder
影响因子：
8.4
作者：
Benz, Sebastian;Mareda, Jiri;Matile, Stefan
通讯作者：
Matile, Stefan