Evans Matthew J, Anker Mathew D, McMullin Claire L, Coles Martyn P
School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington, 6012, New Zealand.
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
Chemistry. 2023 Dec 19;29(71):e202302903. doi: 10.1002/chem.202302903. Epub 2023 Nov 7.
The reaction of 9-diazo-9H-fluorene (fluN ) with the potassium aluminyl K[Al(NON)] ([NON] =[O(SiMe NDipp) ] , Dipp=2,6-iPr C H ) affords K[Al(NON)(κN ,N -{(fluN ) })] (1). Structural analysis shows a near planar 1,4-di(9H-fluoren-9-ylidene)tetraazadiide ligand that chelates to the aluminium. The thermally induced elimination of dinitrogen from 1 affords the neutral aluminium ketimide complex, Al(NON)(N=flu)(THF) (2) and the 1,2-di(9H-fluoren-9-yl)diazene dianion as the potassium salt, [K (THF) ][fluN=Nflu] (3). The reaction of 2 with N,N'-diisopropylcarbodiimide (iPrN=C=NiPr) affords the aluminium guanidinate complex, Al(NON){N(iPr)C(N=CMe )N(CHflu)} (4), showing a rare example of reactivity at a metal ketimide ligand. Density functional theory (DFT) calculations have been used to examine the bonding in the newly formed [(fluN ) ] ligand in 1 and the ketimide bonding in 2. The mechanism leading to the formation of 4 has also been studied using this technique.
9-重氮-9H-芴（fluN）与铝基钾K[Al(NON)]（[NON]=[O(SiMe₂NDipp)₂]，Dipp=2,6-iPr₂C₆H₃）反应生成K[Al(NON)(κN,N -{(fluN)₂})]（1）。结构分析表明，一个近乎平面的1,4-二（9H-芴-9-亚基）四氮二酰亚胺配体螯合到铝上。1经热诱导消除氮气得到中性铝酮亚胺配合物Al(NON)(N=flu)(THF)（2）和作为钾盐的1,2-二（9H-芴-9-基）二氮烯二价阴离子[K₂(THF)₄][fluN=Nflu]（3）。2与N,N'-二异丙基碳二亚胺（iPrN=C=NiPr）反应得到铝胍配合物Al(NON){N(iPr)C(N=CMe₂)N(CHflu)}（4），这是金属酮亚胺配体发生反应的一个罕见例子。密度泛函理论（DFT）计算已用于研究1中新形成[(fluN)₂]配体的键合以及2中酮亚胺的键合。还使用该技术研究了生成
