Synthesis of the first hydroxomonoaryltin(IV) complexes. Crystal and molecular structure of [{Sn[C6H3(NNC6H4Me-4′)-2,Me-5]Cl2(µ-OH)}2]

Abstract
Tin(II) chloride reacts in refluxing xylene with [HgLCl][L = C6H3(NNC6H4R-4′)-2,R-5; R = Me (mpap) or MeO (mopap)] to give metallic mercury and [SnLCl3](L = mpap 1 or mopap 2). Complex 1 reacts with Cl, dimethyl sulfoxide or [Hg(dmap)2](dmap = C6H4CH2NMe2-2) to give, respectively, [Sn(mpap)Cl4]3, [Sn(mpap)Cl3(OSMe2)]4 or [Sn(mpap)(dmap)Cl2]5. Several types of hydrolytic process occur when 1, 2 or [Sn(mpap)Ph2Cl] react with various ligands. Thus, [Hg(dmap)Cl] reacts with 1 or 2 as a base to give [{SnLCl2(µ-OH)}2](L = mpap 6 or mopap 7) and Hg(Hdmap)Cl2. Similarly, PhCH2NMe2(bdma) reacts with 1(1 : 1) to give the hydrolysis product [Hdma][Sn(mpap)Cl3(OH)]8. By treating 6 with excess of NaBr, [{Sn(mpap)Br2(µ-OH)}2]9 can be obtained. Acetic anhydride reacts with complex 6 to give [Sn(mpap)Cl2(O2CMe)]10, but not with 8. The complex [Sn(mpap)Ph2Cl] reacts with Tl(acac)(acac = acetylacetonate), NaH or Ag2O to give the hydrolysis product [Sn(mpap)Ph2(OH)]11. The crystal structure of 6 was determined at –95 °C; the dimeric doubly bridged nature of the compound was confirmed. The Sn–O bridges are asymmetric, the bond lengths depending on the nature of the trans ligand. Two molecules of diethyl ether form hydrogen bonds to the bridging OH groups; another diethyl ether molecule is disordered over a symmetry centre. The structure of compound 7 was also determined; it too is dimeric with two hydroxo bridges, but the refinement was unsatisfactory, probably because of twinning effects.

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