TY - JOUR
T1 - Intermediates and products of the reaction of Zn(ii) organyls with tetrel elementZintlions
T2 - Cluster extensionversuscomplexation
AU - Wallach, C.
AU - Mayer, K.
AU - Henneberger, T.
AU - Klein, W.
AU - Fässler, T. F.
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2020.
PY - 2020/5/21
Y1 - 2020/5/21
N2 - The discovery of low-valent Zn compounds resulted in the renaissance of organometallic Zn complexes. Polyhedral clusters of tetrel elements can interact with Zn atoms either as Lewis donors or by incorporation of the Zn atoms as additional cluster vertices. Herein we report the reactions of ZnR2(R = ethyl (Et), pentamethylcyclopentadiene (Cp*), phenyl (Ph) and 1,3,5-trimethylbenzene (Mes)) withZintlions of the types [E4]4-(E = Ge, Sn) and [Ge9]4-in liquid ammonia. Besides the desiredZintlion complexes, intermediates were isolated that give insight into the reaction of organo Zn compounds in liquid ammonia. Three ions, [(?3:?3-Ge4)(ZnEt)2]2-(1a), [(?2-Sn4)Zn(?2-Sn4)]6-(2a) and [(?4-Ge9)(ZnEt)]3-(3a), were obtained and characterized by means of single crystal X-ray diffraction analysis. Furthermore, amides [(ZnPh2)2(µ2-NH2)2]2-(4a) and {[Zn(µ2-NH2)4][(ZnEt)2(µ2-NH2)2]2}2-(5a) were formed during the reactions, together with the addition products [ZnPh3]-(6a) and [ZnMes3]-(7a) and an anion [Cp*]-(8a), suggesting the following reaction sequence: in liquid ammonia theZintlanions form amides, which then serve as ligands for ZnR2molecules.
AB - The discovery of low-valent Zn compounds resulted in the renaissance of organometallic Zn complexes. Polyhedral clusters of tetrel elements can interact with Zn atoms either as Lewis donors or by incorporation of the Zn atoms as additional cluster vertices. Herein we report the reactions of ZnR2(R = ethyl (Et), pentamethylcyclopentadiene (Cp*), phenyl (Ph) and 1,3,5-trimethylbenzene (Mes)) withZintlions of the types [E4]4-(E = Ge, Sn) and [Ge9]4-in liquid ammonia. Besides the desiredZintlion complexes, intermediates were isolated that give insight into the reaction of organo Zn compounds in liquid ammonia. Three ions, [(?3:?3-Ge4)(ZnEt)2]2-(1a), [(?2-Sn4)Zn(?2-Sn4)]6-(2a) and [(?4-Ge9)(ZnEt)]3-(3a), were obtained and characterized by means of single crystal X-ray diffraction analysis. Furthermore, amides [(ZnPh2)2(µ2-NH2)2]2-(4a) and {[Zn(µ2-NH2)4][(ZnEt)2(µ2-NH2)2]2}2-(5a) were formed during the reactions, together with the addition products [ZnPh3]-(6a) and [ZnMes3]-(7a) and an anion [Cp*]-(8a), suggesting the following reaction sequence: in liquid ammonia theZintlanions form amides, which then serve as ligands for ZnR2molecules.
UR - http://www.scopus.com/inward/record.url?scp=85084964278&partnerID=8YFLogxK
U2 - 10.1039/d0dt01096k
DO - 10.1039/d0dt01096k
M3 - Article
C2 - 32364204
AN - SCOPUS:85084964278
SN - 1477-9226
VL - 49
SP - 6191
EP - 6198
JO - Dalton Transactions
JF - Dalton Transactions
IS - 19
ER -