Compounds containing(pseudo-)tetrahedral main group(semi-)metal units are fundamentally important in three aspects.First,they provide new strategies for the stabilization of tetrahedral units,such as Pn_(4)(Pn=P,As)an...Compounds containing(pseudo-)tetrahedral main group(semi-)metal units are fundamentally important in three aspects.First,they provide new strategies for the stabilization of tetrahedral units,such as Pn_(4)(Pn=P,As)and their isoelectronic analogs,in the coordination sphere of d-/f-block metal atoms.Second,they serve as first-step models for the activation of tetrahedral molecules.Third,they are starting materials for subsequent transformations toward larger clusters or materials.Partial or full isoelectronic replacement of the pnictogen atoms in P4 or As_(4) results in a variety of(pseudo-)tetrahedral anions,Tt_(4)^(4−)(Tt=Si,Ge,Sn,Si/Ge),(Ge_(3)Pn)^(3−)(Pn=P,As;formed in situ),(Tt_(2)Pn_(2))^(2−)(Tt/Pn=Ge/P,Ge/As,Sn/Sb,Sn/Bi,Pb/Sb,Pb/Bi),or(TrBi_(3))^(2−)(Tr=Ga,In,Tl),and also cations,(P3Ch)+(Ch=S,Se,Te).The anions have proven to be excellent starting materials and building blocks for multinary clusters in the context of Zintl chemistry.Such compounds,which push forward the boundary of intriguing P4 chemistry,have never been thoroughly summarized before.In this minireview,we introduce all known intact(pseudo-)tetrahedral group 13–15 units,as well as the coordination compounds based on them,along with two new missing links,[Au(η^(2-)Tt_(2)Bi_(2))_(2)]^(3−)(Tt=Sn,Pb).展开更多
基金supported by the German Research foundation(Deutsche Forschungsgemeinschaft,DFG)F.P.gratefully acknowledges a research fellowship by the Alexander von Humboldt foundation.
文摘Compounds containing(pseudo-)tetrahedral main group(semi-)metal units are fundamentally important in three aspects.First,they provide new strategies for the stabilization of tetrahedral units,such as Pn_(4)(Pn=P,As)and their isoelectronic analogs,in the coordination sphere of d-/f-block metal atoms.Second,they serve as first-step models for the activation of tetrahedral molecules.Third,they are starting materials for subsequent transformations toward larger clusters or materials.Partial or full isoelectronic replacement of the pnictogen atoms in P4 or As_(4) results in a variety of(pseudo-)tetrahedral anions,Tt_(4)^(4−)(Tt=Si,Ge,Sn,Si/Ge),(Ge_(3)Pn)^(3−)(Pn=P,As;formed in situ),(Tt_(2)Pn_(2))^(2−)(Tt/Pn=Ge/P,Ge/As,Sn/Sb,Sn/Bi,Pb/Sb,Pb/Bi),or(TrBi_(3))^(2−)(Tr=Ga,In,Tl),and also cations,(P3Ch)+(Ch=S,Se,Te).The anions have proven to be excellent starting materials and building blocks for multinary clusters in the context of Zintl chemistry.Such compounds,which push forward the boundary of intriguing P4 chemistry,have never been thoroughly summarized before.In this minireview,we introduce all known intact(pseudo-)tetrahedral group 13–15 units,as well as the coordination compounds based on them,along with two new missing links,[Au(η^(2-)Tt_(2)Bi_(2))_(2)]^(3−)(Tt=Sn,Pb).
