Penta‐, Hexa‐, and Heptanuclear Organotin–Oxygen Arsonate Clusters Constructed from an Acetate Drum Cluster Precursor and Different Arsonate Anions

Treatment of the acetate drum [ n BuSn(O)O 2 CMe] 6 withdifferent arsonic acids gave seven organotin arsonate clusters: [( n BuSn) 5 (μ 3 ‐O)(OH)(R′O) 3 (RAsO 3 ) 4 (RAsO 3 H)] [R = 2‐NO 2 C 6 H 4 , R′ = Me ( 1a and 1b )], [( n BuSn) 3 (RAsO 3 )(μ 3 ‐O)(CH 3 CO 2 ) 3 (R′O) 2 ] 2 [R = 2,4‐(NO 2 ) 2 C 6 H 3 , R′ = Me ( 2 )], [( n BuSn) 3 (RAsO 3 ) 2 (RAsO 3 H)(μ 3 ‐O)(R′O) 2 ] 2 [R = 4‐NO 2 C 6 H 4 , R′ = Me ( 3 )], and [( n BuSn) 3 (RAsO 3 ) 3 (μ 3 ‐O)(OH)(R′O) 2 ] 2 Sn [R = C 6 H 5 CH 2 , R′ = Me ( 4 ); R = C 6 H 5 CH 2 , R′ = H ( 5 ); R = C 6 H 5 , R′ = H ( 6 )]. The pentanuclear motif of 1a and 1b , which consists of [Sn 3 (μ 3 ‐O)(μ 2 ‐OR′) 2 ] and [Sn 2 (OH)(μ 2 ‐OR′)] units, was firstly found in organotin compounds. The structures of 2 and 3 possess similar organotin–oxygen clusters. However, the structure of 2 presents the first example of a hexanuclear organotin–oxygen cluster that contains both carboxylate and arsonate ligands. The heptanuclear structures of 4 – 6 , which are composed of two [Sn 3 (μ 3 ‐O)(μ 2 ‐OR′) 2 ] units connected through hydroxy and arsonate ligands to a single tin atom, were firstly obtained by displacement reactions. The syntheses, structures, and structural interrelationship of these diverse organotin–oxygen clusters are also discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)