Bora-amidinate as a cooperative ligand in group 2 metal catalysis.

Bora-amidinate as a cooperative ligand in group 2 metal catalysis.
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硼脒盐作为第 2 族金属催化中的协同配体

DOI:
10.1039/c7dt02136d
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发表时间:
2017
影响因子:
4
通讯作者:
S. Harder
S. Harder
中科院分区:
化学2区
文献类型:
--
作者:
B. Freitag;C. A. Fischer;J. Penafiel;G. Ballmann;H. Elsen;C. Färber;D. Piesik;S. Harder

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介绍了单体硼酰胺酸(bam)配合物DIPPNBN-Mg·(THF)3和DIPPNBN-Ca·(THF)4的合成和晶体结构;DIPPNBN = HB[N(2,6- ipr2 - c6h3)]它们在THF-d8中的1H NMR谱的简单性表明它们的单体固体结构在溶液中保持不变。然而,C6D6中的DIPPNBN-Mg·(THF)3与二聚体处于平衡状态。计算结果(B3PW91/6-311++G**)表明,DIPPNBN-Mg中的N原子具有非常高的局域负电荷(NPA: - 1.103)。bam配体的强碱性与这些配合物在分子内烯烃氢胺化反应中的催化活性一致。提出了bam配体在底物去质子化和产物质子化过程中发挥积极作用的非无辜合作机制。
Syntheses and crystal structures of the monomeric bora-amidinate (bam) complexes DIPPNBN-Mg·(THF)3 and DIPPNBN-Ca·(THF)4 are presented; DIPPNBN = HB[N(2,6-iPr2-C6H3)]2. The simplicity of their 1H NMR spectra in THF-d8 suggest that their monomeric solid state structures are retained in solution. DIPPNBN-Mg·(THF)3 in C6D6, however, is in equilibrium with a dimeric species. Calculations (B3PW91/6-311++G**) reveal a very high localized negative charge (NPA: −1.103) on the N atoms in DIPPNBN-Mg. The strongly basic properties of the bam ligand are in agreement with catalytic activity of these complexes in the intramolecular alkene hydroamination. A mechanism is proposed in which the bam ligand is non-innocent and cooperative, playing an active role in substrate deprotonation and product protonation.
DOI: 10.1002/anie.201105079
发表时间: 2012-01
期刊: Angewandte Chemie
影响因子: --
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