Cid-Seara Krystal M, Pereira-Cameselle Raquel, Bolaño Sandra, Talavera Maria
Departamento de Química Inorgánica, Universidade de Vigo, Campus Universitario, 36310 Vigo, Spain.
Departamento de Química Orgánica, Universidade de Vigo, Campus Universitario, 36310 Vigo, Spain.
Molecules. 2023 Oct 18;28(20):7155. doi: 10.3390/molecules28207155.
Organic amines are important compounds present in a wide variety of products, which makes the development of new systems for their detection an interesting field of study. New organometallic complexes of group 9 [MCpX(2'-R-2-py-SBF)] (M = Ir, Rh; R = H, X = Cl (), R = H, X = OAc (), R = CHO, X = Cl ()), and [IrCpCl(2', 7-diCHO-2-py-SBF)] () (Cp* pentamethylcyclopentadienyl, SBF = 9,9'-spirobifluorene) bearing bidentate C-N ligands based on 9,9'-spirobifluorene were obtained and characterized by NMR spectroscopy, mass spectrometry, IR spectroscopy, and X-ray diffraction analysis when possible. The formation of a Schiff base to give complexes with the formula [MCp*Cl(2'-CH=NR-2-py-SBF)] (M = Ir, Rh; R = alkyl or aryl (-)), through condensation of an amine, and the aldehyde group present in these new complexes was studied leading to a selective reactivity depending on the nature of the amine and the metal center. While the iridium complexes only react with aromatic amines, the rhodium derivative requires heat for those but can react at room temperature with aliphatic amines.
有机胺是存在于多种产品中的重要化合物，这使得开发用于检测它们的新系统成为一个有趣的研究领域。合成了基于9,9'-螺二芴的含双齿C-N配体的第9族新有机金属配合物[MCpX(2'-R-2-py-SBF)]（M = Ir、Rh；R = H，X = Cl ()，R = H，X = OAc ()，R = CHO，X = Cl ()）以及[IrCpCl(2', 7-diCHO-2-py-SBF)] ()（Cp为五甲基环戊二烯基，SBF = 9,9'-螺二芴），并在可能的情况下通过核磁共振光谱、质谱、红外光谱和X射线衍射分析对其进行了表征。研究了通过胺的缩合反应以及这些新配合物中存在的醛基形成席夫碱以生成化学式为[MCpCl(2'-CH=NR-2-py-SBF)]（M = Ir、Rh；R = 烷基或芳基 (-)）的配合物，结果表明反应具有选择性，这取决于胺和金属中心的性质。虽然铱配合物仅与芳香胺反应，但铑衍生物与芳香胺反应需要加热，而与脂肪胺在室温下即可反应。
