The reactions of K_(2)ZnSb(0.234 mol)and Ni(CO)_(2)(PPh_(3))_(2)(x mol)in ethylenediamine(en)solutions of 18-crown-6 at 60℃yielded half-centered[Ni_(0.5)@{Sb_(6)Ni_(6)(CO)_(8)}]_(4)-(x=0.023,1)and fully embedded[Ni@{...The reactions of K_(2)ZnSb(0.234 mol)and Ni(CO)_(2)(PPh_(3))_(2)(x mol)in ethylenediamine(en)solutions of 18-crown-6 at 60℃yielded half-centered[Ni_(0.5)@{Sb_(6)Ni_(6)(CO)_(8)}]_(4)-(x=0.023,1)and fully embedded[Ni@{Sb_(7)Ni_(5)(CO)_(6)}]^(3-)(x=0.047,2),wherein the chair-like Sb_(6)subunit is bicapped by two Ni_(3) triangles to form the single Sb_(6)Ni_(6) icosahedron of 1 and by the triangular Ni_(2)Sb and Ni_(3) to form the single Sb_(7)Ni_(5) icosahedron of 2.Surprisingly,a smaller amount of Ni(CO)_(2)(PPh_(3))_(2)(x=0.016)led to the formation of the unprecedented dimer[(Sb_(8)){Sb_(7)Ni_(5)(CO)_(4)}_(2)]^(6-)(4),wherein the Sb_(7)Ni_(5) icosahedral unit built of boat-like Sb_(6),Ni_(2)Sb and Ni_(3) is linked together by the realgar-like Sb_(8) to form the icosahedral dimer 4,providing a new way of thinking for the preparation of icosahedral oligomers/polymers.A similar hexa-anionic dimer(3)can be solely obtained using PBu^(4+)as the countercation under the same reaction conditions.The structure and bonding of this novel series of icosahedral clusters containing polyantimony were discussed for the first time.展开更多
Binary polyantimony clusters,namely[Cu_(2)Sb_(14)]^(4–) and [Ag_(2)Sb_(14)]^(4–),containing coinage metals,were successfully synthesized and characterized,in which two homoatomic Sb73–subunits are bridged by two co...Binary polyantimony clusters,namely[Cu_(2)Sb_(14)]^(4–) and [Ag_(2)Sb_(14)]^(4–),containing coinage metals,were successfully synthesized and characterized,in which two homoatomic Sb73–subunits are bridged by two coinage metals in η^(4):η^(1) and η^(1):η^(1) coordination modes,respectively.In[M_(2)Sb_(14)]^(4-),two bridging Cu ions and two Sb atoms form a planar rhombic unit,which was revealed to have antiaromatic properties by theoretical calculations.Further electron structure and bonding analysis confirmed the presence of delocalized bonds in the rhombic unit and the metallophilic interaction between two formal M^(+) ions.展开更多
基金supported by the National Natural Science Foundation of China(21873102).
文摘The reactions of K_(2)ZnSb(0.234 mol)and Ni(CO)_(2)(PPh_(3))_(2)(x mol)in ethylenediamine(en)solutions of 18-crown-6 at 60℃yielded half-centered[Ni_(0.5)@{Sb_(6)Ni_(6)(CO)_(8)}]_(4)-(x=0.023,1)and fully embedded[Ni@{Sb_(7)Ni_(5)(CO)_(6)}]^(3-)(x=0.047,2),wherein the chair-like Sb_(6)subunit is bicapped by two Ni_(3) triangles to form the single Sb_(6)Ni_(6) icosahedron of 1 and by the triangular Ni_(2)Sb and Ni_(3) to form the single Sb_(7)Ni_(5) icosahedron of 2.Surprisingly,a smaller amount of Ni(CO)_(2)(PPh_(3))_(2)(x=0.016)led to the formation of the unprecedented dimer[(Sb_(8)){Sb_(7)Ni_(5)(CO)_(4)}_(2)]^(6-)(4),wherein the Sb_(7)Ni_(5) icosahedral unit built of boat-like Sb_(6),Ni_(2)Sb and Ni_(3) is linked together by the realgar-like Sb_(8) to form the icosahedral dimer 4,providing a new way of thinking for the preparation of icosahedral oligomers/polymers.A similar hexa-anionic dimer(3)can be solely obtained using PBu^(4+)as the countercation under the same reaction conditions.The structure and bonding of this novel series of icosahedral clusters containing polyantimony were discussed for the first time.
基金supported by the National Natural Science Foundation of China(Nos.92161102,22371140 to Z.-M.Sun and 22301143 to L.Qiao)the Fundamental Research Program of Shanxi Province(202103021224028 and 202204021301010 to W.-J.Tian)the Natural Science Foundation of Tianjin City(21JCZXJC00140 to Z.-M.Sun).
文摘Binary polyantimony clusters,namely[Cu_(2)Sb_(14)]^(4–) and [Ag_(2)Sb_(14)]^(4–),containing coinage metals,were successfully synthesized and characterized,in which two homoatomic Sb73–subunits are bridged by two coinage metals in η^(4):η^(1) and η^(1):η^(1) coordination modes,respectively.In[M_(2)Sb_(14)]^(4-),two bridging Cu ions and two Sb atoms form a planar rhombic unit,which was revealed to have antiaromatic properties by theoretical calculations.Further electron structure and bonding analysis confirmed the presence of delocalized bonds in the rhombic unit and the metallophilic interaction between two formal M^(+) ions.
