Stannaborate Chemistry: Nucleophilic Substitution at the Cluster Sphere

Abstract

Nucleophilic substitution at (γ‐chloropropyl)stanna‐closododecaborate [Cl(CH2)3SnB11H11]− with RLi [R = Ph, Me2NC6H4, ferrocenyl (Fc)] and RMgBr (R = vinyl, benzyl) affords the substitution products containing the anion [RSnB11H11]−. The reaction products have been characterized by elemental analysis, NMR spectroscopy and in the cases where R = Ph, Me2NC6H4, Fc and vinyl by X‐ray structure analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Stanna-closo-dodecaborate Chemistry

“…During our alkylation studies, we discovered that the (γchloropropyl)stannaborate [Cl(CH 2 ) 3 -SnB 11 H 11 ] -, which can be prepared by reaction of stannadodecaborate with 1-chloro-3-iodopropane, undergoes a nucleophilically induced elimination of the γ-chloropropyl group when treated with alkyllithium or aryllithium reagents (Scheme 3). 69 The phenylated stannaborate [C 6 H 5 SnB 11 H 11 ]could be prepared using this protocol. Furthermore, nucleophilic displacement of the γ-chloropropyl group also was possible with NaH, which generated the unsubstituted stannaborate [SnB 11 H 11 ] 2-.…”

Anionic Phosphane − A New Ligand with a Phosphane and a Weakly Coordinating Heteroborate Moiety

“…[12] Attack at the γ-chloropropyl-substituted cluster 1 with strong nucleophiles like RLi or RMgX resulted in the isolation of derivatives [RSnB 11 H 11 ] Ϫ together with the formation of cyclopropane and the chloride anion as the leaving groups (Scheme 1). The new phosphane 2 was characterized by NMR spectroscopy and X-ray structure analysis.…”

Self-doping of molecular quantum-dot cellular automata: mixed valence zwitterions

“…To date most studies of zwitterionic metallocene catalysts have been limited to systems containing a single boron atom, [43][44][45][46] although dianion boron clusters have been introduced in the chemistry of transition-metal zwitterions very recently. [47][48][49][50] Monoborane systems have a relatively small spatial volume and thus a weak ability to hold extra electrons. It is possible that many complexes thought to be zwitterionic are in fact stabilized by non-zwitterionic resonance or by partial hapticity.…”