From Dibismuthenes to Three- and Two-Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study.
From Dibismuthenes to Three- and Two-Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study.
复制标题
通过精细配体调节从二铋烯到三配位和二配位铋烯：通过实验和理论相结合的研究证明芳香族 BiC3N 环的证据。
作者：
Iva Vránová;M. Alonso;Rabindranath Lo;R. Sedlak;R. Jambor;A. Růžička;F. de Proft;P. Hobza;Libor Dostál
N，C，N-螯合氯化铋[C6 H3 - 2，6-（CH=NR）2] BiCl 2 [其中R = tBu（1），2 '，6'-Me 2C 6 H3（2）或4 '-Me 2NC 6 H4（3）]或N，C-螯合类似物[C6 H2 -2，6-（CH = NR）2]的还原报道了（CH=N-2 '，6'-iPr_2C_6H_3）-4，6-（tBu）_2] BiCl_2（4）和[C_6H_2 -2-（CH_2NEt_2）-4，6-（tBu）_2] BiCl_2（5）。化合物1-3的还原得到单体N，C，N-螯合的铋杂环丁烷[C6 H3 - 2，6-（CH=NR）2]Bi [其中R = tBu（6），2 ′，6 ′-Me 2C 6 H3（7）或4 ′-Me 2NC 6 H4（8）]。类似地，4的还原导致化合物[C6 H2 -2-（CH=N-2 '，6'-iPr 2C 6 H3）-4，6-（tBu）2]Bi（9）的分离，其为已在结构上表征的前所未有的双配位亚铋。与此相反，二铋烯{[C6 H2 -2-（CH 2NEt 2）-4，6-（tBu）2]Bi}2（10）是通过还原5得到的。化合物6-10用（1）H和（13）C NMR谱进行了表征，除7外，其结构用单晶X射线衍射分析确定。 很明显，还原产物的结构（偏铋烯与二铋烯）是配体依赖性的，特别是受到N→Bi分子内相互作用强度的影响。因此，包括描述所研究化合物和相关铋（I）体系中成键情况的理论调查。重要的是，我们发现，C3 NBi螯合环中的两个协调的bismuthinidene 9表现出显着的芳香族特征的铋孤对离域。
The reduction of N,C,N-chelated bismuth chlorides [C6H3-2,6-(CH=NR)2]BiCl2 [where R = tBu (1), 2',6'-Me2C6H3 (2), or 4'-Me2NC6H4 (3)] or N,C-chelated analogues [C6H2-2-(CH=N-2',6'-iPr2C6H3)-4,6-(tBu)2]BiCl2 (4) and [C6H2-2-(CH2NEt2)-4,6-(tBu)2]BiCl2 (5) is reported. Reduction of compounds 1-3 gave monomeric N,C,N-chelated bismuthinidenes [C6H3-2,6-(CH=NR)2]Bi [where R = tBu (6), 2',6'-Me2C6H3 (7) or 4'-Me2NC6H4 (8)]. Similarly, the reduction of 4 led to the isolation of the compound [C6H2-2-(CH=N-2',6'-iPr2C6H3)-4,6-(tBu)2]Bi (9) as an unprecedented two-coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C6H2-2-(CH2NEt2)-4,6-(tBu)2]Bi}2 (10) was obtained by the reduction of 5. Compounds 6-10 were characterized by using (1)H and (13)C NMR spectroscopy and their structures, except for 7, were determined with the help of single-crystal X-ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand-dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C3NBi chelating ring in the two-coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair.
影响因子：
16.6
作者：
Ganesamoorthy, Chelladurai;Blaeser, Dieter;Schulz, Stephan
通讯作者：
Schulz, Stephan