摘要
The endohedral plumbaspherene cluster anion [Rh@Pbl2]3- was synthesized by the reaction of K4Pb9 with Rh(PPh3)3Cl in ethylenediamine (en) solution in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), and characterized by single-crystal X-ray diffraction and energy-dispersive X-ray (EDX) analysis. The novel zintl ion cluster [Rh@Pbl2]^- represents the first structurally characterized plumbaspherene Pb12 cluster with Ih point symmetry encapsulating a group 9 element in a spherical tetrel deltahedron. And the discovery of anion [Rh@Pb12]3- also provides direct proof for previous reports on the observation of [M@Pb12]x± (clusters in mass spectrometric experiments proved by quantum-chemical calculations). DFT computations indicate that the icosahedral cluster anion [Rh@Pb12]3- is isostructural and isoelectronic with [Ir@Sn12]3-.
The endohedral plumbaspherene cluster anion [Rh@Pbl2]3- was synthesized by the reaction of K4Pb9 with Rh(PPh3)3Cl in ethylenediamine (en) solution in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), and characterized by single-crystal X-ray diffraction and energy-dispersive X-ray (EDX) analysis. The novel zintl ion cluster [Rh@Pbl2]^- represents the first structurally characterized plumbaspherene Pb12 cluster with Ih point symmetry encapsulating a group 9 element in a spherical tetrel deltahedron. And the discovery of anion [Rh@Pb12]3- also provides direct proof for previous reports on the observation of [M@Pb12]x± (clusters in mass spectrometric experiments proved by quantum-chemical calculations). DFT computations indicate that the icosahedral cluster anion [Rh@Pb12]3- is isostructural and isoelectronic with [Ir@Sn12]3-.
基金
supported by the National Natural Science Foundation of China(No.21473200)