芴衍生鋁三價錯合物之合成，鑑定及其反應性研究

Study of Synthesis, Characterization and Reactivity of Fluorenyl Aluminum(III) Complexes

黃珞蕎(Hwang, Robin Christine)

指導教授 ： 劉學儒

國立交通大學/理學院/應用化學系所/碩士(2018年)

摘要

本篇研究主旨在於嘗試合成以雙叔丁基芴 (1; 2,7-di-tert-butyl-9H-fluorene) 為配基
的低價數鋁錯合物。我們首先合成出了 FluoAlCl2(OEt2) (2, Fluo=ditbutylfluorenyl)，然後使
用鉀石墨還原得到了其他三價鋁錯合物 Fluo2AlCl(OEt2) (3)，[Fluo3AlKCl(OEt2)] (4) 與
Fluo3Al(OEt2) (5)。此外，我們合成了三芴取代的配位基 H3L1 以及 H3L2。不同的胺鋰鹽
和 2 混 和 後 得 到 了 FluoAlClN(SiMe3)2(THF) (6) ， FluoAl(N(SiMe3)2)2 (7) ，
FluoAlCl(NiPr2)(OEt2) (8) 和 FluoAl(NHDipp)2(OEt2) (9)。我們把含有立障的氮異環碳烯配基
(N-heterocyclic Carbene)像是 IMes (1,3-bis(2,4,6-trimethylphenyl)imidazolylidene)以及 IPr
(1,3-Bis-(2,6-diisopropylphenyl)imidazole-ylidene)混和 後會得到 FluoAl(IMes)Cl2 (10) 和
FluoAl(IPr)Cl2 (11)。FluoAlH2(OEt2) (12)是由 3 與等當量的氫化鋁鋰(lithium aluminum
hydride)混合而成。12 和等當量的 4-二甲氨基吡啶(dmap = 4-dimethylaminopyridine)反應形
成 FluoAl(dmap)H2 (13)。 6, 7, 8 和 9的鉀石墨還原並沒有得到乾淨及可分離的產物，而 10
和 11 的鉀石墨還原則得到了鉀芴鹽(KFluo)以及一組含有 Al-NHC 產物。13 在加熱時會釋
放雙叔丁基芴(1)，暗示鋁金屬中心可能具有還原脫去之特性。

關鍵字

鋁 ； 金屬錯合物 ； 低價數鋁

並列摘要

The motivation of this research is to synthesize the low-valent aluminum complexes
supported by 2,7-di-tert-butyl-9H-fluorenyl ligand. FluoAlCl2(OEt2) (2, Fluo=ditbutylfluorenyl)
was first synthesized then reduced by KC8 (potassium graphite) to form Fluo2AlCl(OEt2) (3),
[Fluo3AlKCl(OEt2)] (4) and Fluo3Al(OEt2) (5). Another strategy was taken to synthesize a group
of tris-fluorenyl ligands: H3L1 and H3L2. Numerous amides were mixed with 2 to form
FluoAlCl(N(SiMe3)2)(THF) (6) FluoAl(N(SiMe3)2)2 (7), FluoAlCl(NiPr2)(OEt2) (8) and
FluoAl(NHDipp)2(OEt2) (9). Bulky NHC (N-heterocyclic) carbene like IMes (1,3-bis(2,4,6
trimethylphenyl)imidazolylidene) and IPr (1,3-Bis-(2,6-diisopropylphenyl)imidazole-ylidene)
were also mixed with 2 to form FluoAl(IMes)Cl2 (10) and FluoAl(IPr)Cl2 (11). FluoAlH2(OEt2)
(12) was formed by mixing 3 with one equiv. of LAH (lithium aluminum hydride).
FluoAl(dmap)H2 (13, dmap = 4-dimethylaminopyridine) was then synthesized by mixing 12 with
one equiv. of dmap. Reduction of 6, 7, 8 and 9 using KC8 resulted in a group of unclean spectra.
KFluo, the potassium salt and an unidentified Al(NHC) species were found after the KC8 reduction
of 10 and 11. 13 tended to release free ditbutylfluorene (1) upon heating, likely resulting from
reductive elimination at Al center.

並列關鍵字

aluminum ； complexes ； low-valent aluminum complexes

參考文獻

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