An adamantane-shaped, ferrocenyl-substituted tin selenide complex, [(FcSn)4Se6] (1; Fc = ferrocenyl), and a ferrocenyl-substituted tin telluride five-membered ring, [(Fc2Sn)3Te2] (2), were obtained upon treatment of FcSnCl3 with K2E (E = Se, Te). Complex 1 further reacts with Na2S·9H2O and [Cu(PPh3)3Cl] to form a ternary complex, [(CuPPh3)6(S/Se)6(SnFc)2] (3). We discuss structures, optical and electrochemical properties as well as Mössbauer spectra.

Three organotin-oxido clusters were formed by hydrolysis of ferrocenyl-functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [R(Fc) SnCl3 ⋅HCl] (C; R(Fc) = CMe2 CH2 C(Me)=N-N=C(Me)Fc) and [SnCl6 ](2-) formed {(R(Fc) SnCl2 )3 [Sn(OH)6 ]}[SnCl3 ] (3 a) and {(R(Fc) SnCl2 )3 [Sn(OH)6 ]}[PhSeO3 ] (3 b), bearing an unprecedented [Sn4 O6 ] unit, in a one-pot synthesis or stepwise through [(R(Fc) SnCl2 )2 Se] (1) plus [(R(Fc) SnCl2 )SePh] (2). A one-pot reaction starting out from FcSnCl3 gave [(FcSn)9 (OH)6 O8 Cl5 ] (4), which represents the largest Fc-decorated Sn/O cluster reported to date.

Dedication to Prof. Schnöckel on the Occasion of his 80th BirthdayA series of alkaline metal functionalised tert-butyl substituted bis(amido)diazadiarsetidinides [(μ-N(tBu)As) 2 (N(tBu)M) 2 ] (M = K (1), Rb (2), Cs (3), Na•thf (4), Na (5)) were prepared and their solid state structures investigated in detail. Further substitution reactions with tert-butyl substituted element chlorides of P, As, Sb and Bi were performed. The conversion of two equivalents tBu 2 AsCl (II) with 1-3 unexpectedly leads to the introduction of only one arsine moiety ([(μ-N(tBu)As) 2 (N(tBu)H)(N(tBu)AstBu 2 ] (6)) while the other nitrogen atom gets protonated by ether cleavage. The reaction of one equivalent tBuECl 2 (E = As (III), Sb (IV)) with 1, 2 or 3 yielded the intended cage compounds [(μ-N(tBu)As) 2 (NtBu) 2 EtBu] (E = As (7), Sb ( 8)) in high yields. Reaction of 1-3 with two equivalents of tBu 2 E'Cl (E' = Sb (V), Bi (VI)) yields the twofold substituted bis(amido)diazadiarsetidines [(μ-N(tBu) As) 2 (N(tBu)E'tBu 2 ) 2 ] (E' = Sb (9), Bi (10)), which show weak intramolecular E'-E' interactions.