Quintero Gabriela Espinoza, Paterson-Taylor Isabelle, Rees Nicholas H, Goicoechea Jose M
Department of Chemistry and University of Oxford and Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Dalton Trans. 2016 Feb 7;45(5):1930-6. doi: 10.1039/c5dt02380g. Epub 2015 Jul 24.
Reactions of the protonated heptaphosphide dianion, HP7, with one equivalent of E[N(SiMe3)2]2 (E = Ge, Sn, Pb) give rise to novel derivatized cluster anions P7EN(SiMe3)2 (E = Ge (1), Sn (2) and Pb (3)). All three species were characterized by multi-element solution-phase NMR spectroscopy and electrospray ionization mass spectrometry. In addition, 1 and 2 were structurally authenticated by means of single crystal X-ray diffraction in [K(18-crown-6)]2[P7EN(SiMe3)2]·2py. Interestingly, while 2 appears to be indefinitely stable in solution for prolonged periods of time, the germanium-containing analogue, 1, readily decomposes at room temperature giving rise to the dimeric species (P7Ge)2N(SiMe3)2 (4) and [K(18-crown-6)][N(SiMe3)2]. A low quality single crystal X-ray structure of the former allowed for the confirmation of its composition and connectivity which is consistent with the (31)P NMR spectrum obtained for the anion.
质子化的七磷化物二价阴离子HP7与一当量的E[N(SiMe3)2]2（E = Ge、Sn、Pb）反应生成新型衍生化簇阴离子P7EN(SiMe3)2（E = Ge (1)、Sn (2) 和Pb (3)）。所有这三种物质均通过多元素溶液相核磁共振光谱和电喷雾电离质谱进行了表征。此外，1和2通过在[K(18-冠-6)]2[P7EN(SiMe3)2]·2py中进行单晶X射线衍射进行了结构鉴定。有趣的是，虽然2在溶液中似乎能长时间无限稳定，但含锗类似物1在室温下很容易分解，生成二聚体(P7Ge)2N(SiMe3)2 (4) 和[K(18-冠-6)][N(SiMe3)2]。前者的低质量单晶X射线结构证实了其组成和连接性，这与为该阴离子获得的(31)P NMR光谱一致。
