Synthesis and reactivity of fluorenyl-tethered N-heterocyclic stannylenes.
Synthesis and reactivity of fluorenyl-tethered N-heterocyclic stannylenes.
复制标题
DOI：
10.1039/c5dt04060d
复制
发表时间：
2016-03
影响因子：
4
通讯作者：
Marta Roselló-Merino;S. M. Mansell
中科院分区：
文献类型：
--
作者：
Marta Roselló-Merino;S. M. Mansell
以二异丙基苯基(DIPP)取代的二胺与(溴乙基)荧经亲核取代反应合成了二芳基(F1)二胺，以较高的产率(85%)合成了FlC2H4N(H)C2H4N(H)DIPP(1a)。1a与n-BuLi的锂离子配位到芳香族荧环(2)，然后与n-BuLi的等价物，仲胺依次去质子化。将1a与SnN‘’2{N‘’=N(SiMe3)2}作为中性二聚物(5)反应，合成了一种荧基栓系的N-杂环锡烯(NHSN)，并用LIN‘’对其进行去质子化，得到相应的二阴离子荧烷系留的NHSN(6).[{Rh(Cod)(μ-Cl)}2]与单脱质子配体2反应生成混合给体胺-Rh(I)Rh(I)化合物(7)，而与阴离子NHSN6反应生成低稳定性的非配位NHSN侧臂的Rh-荧基配合物，X-射线晶体分析表明该配合物在固态下为二聚体。
A fluorenyl (Fl) tethered diamine was synthesised by nucleophilic substitution of (bromoethyl)fluorene with a diisopropylphenyl (Dipp) substituted diamine to give FlC2H4N(H)C2H4N(H)Dipp (1a) in good yield (85%). Lithiation of 1a with n-BuLi proceeded with coordination of the Li cation to the aromatic fluorenide ring (2), and with subsequent equivalents of n-BuLi, the secondary amines were then sequentially deprotonated. A fluorenyl-tethered N-heterocyclic stannylene (NHSn) was synthesised from the reaction of 1a with SnN''2 {N'' = N(SiMe3)2} as a neutral dimeric species (5), and this was deprotonated with LiN'' to give the corresponding dianionic fluorenide-tethered NHSn (6). Reactions of [{Rh(cod)(μ-Cl)}2] with the mono-deprotonated ligand 2 led to the formation of a mixed-donor amide-amine Rh(i) compound (7), whereas reactions with the anionic NHSn 6 led to a Rh-fluorenyl complex of low stability with an uncoordinated pendent NHSn arm, which X-ray crystallography showed to be dimeric in the solid state.