Transition Metal‐Assisted Hydrolysis of Pyrazole‐Appended Organooxotin Carboxylates Accompanied by Ligand Transfer

The reaction of the potentially multi‐site coordination ligands [{ n Bu 2 SnO 2 CL} 2 O] 2 ( 1 ), [{ n Bu 2 SnO 2 CL′} 2 O] 2 ( 2 ), [ n BuSn(O)O 2 CL] 6 ( 3 ), and [ n BuSn(O)O 2 CL′] 6 ( 4 ), (L = (Pz) 2 CH‐); L′ = (3,5‐Me 2 Pz) 2 CH‐; Pz = pyrazolyl) with hydrated metal salts leads to the hydrolysis of the organotin carboxylates accompanied by the formation of insoluble organotinoxide/hydroxides and metal complexes. The in situ generated LCOO and L′COO ligands bind to the metal ions. The complexes [Cu(LCOO) 2 (NO 3 ) 2 ( n Bu 2 Sn((H 2 O) 2 )] n [Cu(LCOO) 2 ] ( 5 ), [Mg(L′COO) 2 ] ( 6 ), [Cu(LCOO) 2 ] ( 7 ), and [{(Cu(L′COO) 2 (Cu(MeOH)) 3 }{ClO 4 } 2 ] n ( 8 ) were isolated and structurally characterized. The solid‐state structure of 5 reveals that two discrete molecules are present in the same asymmetric unit; a heterobimetallic coordination polymer, [Cu(LCOO) 2 (NO 3 ) 2 ( n Bu 2 Sn((H 2 O) 2 )] n and a discrete coordination complex, [Cu(LCOO) 2 ]. The cationic portion of the heterobimetallic compound contains alternate six‐coordinate Sn IV and Cu II centers bridged by the carboxylate oxygen atoms of the LCOO ligand.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)