The reactions of K_(5)Pn_(4)(Pn=Sb and Bi)and CpRh(PPh_(3))_(2)(Cp=C_(5)H_(5),cyclopentadiene)in ethylenediamine(en)solutions resulted in a series of new Pn_(7)^(3−)−adducts,{Pn_(8)[Rh(PPh_(3))]_(2)}^(2−),{Sb_(7)[Rh(P...The reactions of K_(5)Pn_(4)(Pn=Sb and Bi)and CpRh(PPh_(3))_(2)(Cp=C_(5)H_(5),cyclopentadiene)in ethylenediamine(en)solutions resulted in a series of new Pn_(7)^(3−)−adducts,{Pn_(8)[Rh(PPh_(3))]_(2)}^(2−),{Sb_(7)[Rh(PPh_(3))]_(2)}^(2)−,and{Sb_(7)[Rh(PPh_(3))]_(3)}^(2−),through slight variations in reaction conditions.These clusters represent rare electron-deficient group 15 polyhedral clusters comprising Pn_(7)^(3−)−with RhPPh3 units in anη^(5)coordination mode.Notably,the anionic clusters{Sb_(8)[Rh(PPh_(3))]_(2)}^(2−),{Sb_(7)[Rh(PPh_(3))]_(2)}^(2−),and{Sb_(7)[Rh(PPh_(3))]_(3)}^(2−)are the first Rh-Sb binary Zintl clusters to date.The synthesis,structure,and bonding of these new deltahedral hybrids were studied for the first time,revealing a highly versatile chemistry associated with classical Pn_(7)^(3−)−cages and offering a pathway to prepare polyhedral hybrid clusters based on Pn_(7)^(3−)−cages.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22425107,92461303,22371140,and 92161102(Z.-M.S.))and(No.22301143(L.Q.)).
文摘The reactions of K_(5)Pn_(4)(Pn=Sb and Bi)and CpRh(PPh_(3))_(2)(Cp=C_(5)H_(5),cyclopentadiene)in ethylenediamine(en)solutions resulted in a series of new Pn_(7)^(3−)−adducts,{Pn_(8)[Rh(PPh_(3))]_(2)}^(2−),{Sb_(7)[Rh(PPh_(3))]_(2)}^(2)−,and{Sb_(7)[Rh(PPh_(3))]_(3)}^(2−),through slight variations in reaction conditions.These clusters represent rare electron-deficient group 15 polyhedral clusters comprising Pn_(7)^(3−)−with RhPPh3 units in anη^(5)coordination mode.Notably,the anionic clusters{Sb_(8)[Rh(PPh_(3))]_(2)}^(2−),{Sb_(7)[Rh(PPh_(3))]_(2)}^(2−),and{Sb_(7)[Rh(PPh_(3))]_(3)}^(2−)are the first Rh-Sb binary Zintl clusters to date.The synthesis,structure,and bonding of these new deltahedral hybrids were studied for the first time,revealing a highly versatile chemistry associated with classical Pn_(7)^(3−)−cages and offering a pathway to prepare polyhedral hybrid clusters based on Pn_(7)^(3−)−cages.
