Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible in...Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible intermediate,cluster 1,was isolated from the solution phase through subtle changes in reaction conditions in the formation process of complex 2.Hence,we establish the pathway of the bimetallic bridged clusters[Cu_(2)As_(14)]^(4-)by the oxidation of the[As_(7)Cu(PPh_(3))]^(2-).Quantum chemical calculations reveal the presence of metallophilic interaction in clusters 2 and 3.展开更多
In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of...In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms.The single-crystal X-ray diffraction(XRD)analysis reveals the dimeric nature of the clusters.Two different assembly patterns of the formal[Sn(η^(3)-Sn_(9))]monomer were observed:the dimerization through the vertex fusion process and the direct dimerization through the formation of 2c–2e Sn–Snσbond.For both clusters,the density functional theory calculations reveal the locallyσ-aromatic nature of the[Sn(η^(3)-Sn_(9))]monomer resulting in two independent magnetic shielding cones.We believe that our findings will help the community to further explore the fascinating chemistry of polystannide clusters.展开更多
基金supported by the National Natural Science Foundation of China(21971118 to Z.-M.S.).
文摘Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible intermediate,cluster 1,was isolated from the solution phase through subtle changes in reaction conditions in the formation process of complex 2.Hence,we establish the pathway of the bimetallic bridged clusters[Cu_(2)As_(14)]^(4-)by the oxidation of the[As_(7)Cu(PPh_(3))]^(2-).Quantum chemical calculations reveal the presence of metallophilic interaction in clusters 2 and 3.
基金supported by the National Natural Science Foundation of China(Nos.92161102 and 21971118)the Natural Science Foundation of Tianjin City(Nos.20JCYBJC01560 and B2021202077)+2 种基金Z.M.S.A.I.B.acknowledges financial support from the R.Gaurth Hansen Professorship fundThe support and resources from the Centre for High Performance Computing at the University of Utah are gratefully acknowledged.A.M.C.acknowledges financial support from FONDECYT 1180683We also thank the valuable discussion from Professor Slavi C.Sevov(Department of Chemistry and Biochemistry,University of Notre Dame).
文摘In this work,we report the synthesis and characterization of two novel Ru-containing Zintl clusters:[Sn_(19){Ru(COD)(en)}_(2)]^(4−)and[Sn_(20){Ru(COD)}_(2)]^(6−).The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms.The single-crystal X-ray diffraction(XRD)analysis reveals the dimeric nature of the clusters.Two different assembly patterns of the formal[Sn(η^(3)-Sn_(9))]monomer were observed:the dimerization through the vertex fusion process and the direct dimerization through the formation of 2c–2e Sn–Snσbond.For both clusters,the density functional theory calculations reveal the locallyσ-aromatic nature of the[Sn(η^(3)-Sn_(9))]monomer resulting in two independent magnetic shielding cones.We believe that our findings will help the community to further explore the fascinating chemistry of polystannide clusters.
