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On the Reactivity of Silylated Ge 9 Clusters: Synthesis and Characterization of [ZnCp*(Ge 9 {Si(SiMe 3 ) 3 } 3 )], [CuP i Pr 3 (Ge 9 {Si(SiMe 3 ) 3 } 3 )], and [(CuP i Pr 3 ) 4 {Ge 9 (SiPh 3 ) 2 } 2 ]
Author(s) -
Mayer Kerstin,
Schiegerl Lorenz J.,
Fässler Thomas F.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603475
Subject(s) - reactivity (psychology) , chemistry , zintl phase , crystallography , tris , stoichiometry , isopropyl , cluster (spacecraft) , germanium , stereochemistry , medicinal chemistry , silicon , crystal structure , organic chemistry , medicine , biochemistry , alternative medicine , pathology , computer science , programming language
We report on the synthesis of new derivatives of silylated clusters of the type [Ge 9 (SiR 3 ) 3 ] − (R = SiMe 3 , Me = CH 3 ; R = Ph, Ph = C 6 H 5 ) as well as on their reactivity towards copper and zinc compounds. The silylated cluster compounds were synthesized by heterogeneous reactions starting from the Zintl phase K 4 Ge 9 . Reaction of K[Ge 9 {Si(SiMe 3 ) 3 } 3 ] with ZnCl 2 leads to the already known dimeric compound [Zn(Ge 9 {Si(SiMe 3 ) 3 } 3 ) 2 ] ( 1 ), whereas upon the reaction with [ZnCp* 2 ] the coordination of [ZnCp*] + to the cluster takes place (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) under the formation of [ZnCp*(Ge 9 {Si(SiMe 3 ) 3 } 3 )] ( 2 ). A similar reaction leads to [CuP i Pr 3 (Ge 9 {Si(SiMe 3 ) 3 } 3 )] ( 3 ) from [CuP i Pr 3 Cl] ( i Pr=isopropyl). Further we investigated the novel silylated cluster units [Ge 9 (SiPh 3 ) 3 ] − ( 4 ) and [Ge 9 (SiPh 3 ) 2 ] − ( 5 ), which could be identified by mass spectroscopy. Bis‐ and tris‐silylated species can be synthesized by the respective stoichiometric reactions, and the products were characterized by ESI‐MS and NMR experiments. These clusters show rather different reactivity. The reaction of the tris‐silylated anion 4 with [CuP i Pr 3 Cl] leads to [(CuP i Pr 3 ) 3 Ge 9 (SiPh 3 ) 2 ] + as shown from NMR experiments and to [(CuP i Pr 3 ) 4 {Ge 9 (SiPh 3 ) 2 } 2 ] ( 6 ), which was characterized by single‐crystal X‐ray diffraction. Compound 6 shows a new type of coordination of the Cu atoms to the silylated Zintl clusters.