A series of nine novel diorganotin(IV) complexes of O,N,O' chelating ligands were synthesized viz., [n-Bu₂Sn(L²)]₂·0.25 (C₆H₁₄) (1), [Me₂Sn(L¹)]₂·(C₇H₈) (2), [n-Bu₂Sn(L¹)]₂·(C₇H₈) (3), [Me₂Sn(L³)]₂·(C₇H₈) (4), 2 [n-Bu₂Sn(L³)]₂·4 (n-Bu₂Sn(L³)) (5), [Ph₂Sn(L³)] (6), [Ph₂Sn(L¹)] (7), [Ph₂Sn(L⁴)] (8) and [Ph₂Sn(L²)] (9) and structurally characterized. The ligand scaffolds differ with respect to the chemical link between the coordinating N and O atoms, which is either an alkyl or an aryl moiety. Diffraction results indicate that the smallest methyl groups favor dimerization via Sn–O–Sn bridging and six-coordination at the cation. Among these dinuclear derivatives, more asymmetric oxygen bridges and longer Sn⋯Sn separations are found for the less nucleophilic phenolate O. In contrast, the bulky phenyl substituents prevent aggregation for both classes of ligands and always lead to five-coordinated mononuclear species. The n-Bu groups are sterically more demanding than Me but flexible, resulting in an intermediate behavior. When the O,N,O' ligand with phenolate O coordinates a Sn(n-Bu)₂ fragment, a borderline situation occurs and both mono- and dinuclear complexes coexist in the same crystalline solid. The overall structural variety is reflected in a range of different Addison-τ₅ [Addison et al., J. Chem. Soc., Dalton Trans. 1984, 1349-1356] descriptors for five-fold coordination. For better comparability we introduce a slightly modified geometry index τ'₅, in which the basal angle α is subtended by the organic substituents, regardless of its absolute value. τ'₅ represents a sensitive indicator for the coordination geometry about Sn^IV. Tin NMR results revealed that all compounds exist as mononuclear pentacoordinated species in solution.

合成了O，N，O ′螯合配体的一系列九种新颖的二有机锡（IV）配合物。，[ n -Bu ₂ Sn（L ²）] ₂ ·0.25（C ₆ H ₁₄）（1），[Me ₂ Sn（L ¹）] ₂ ·（C ₇ H ₈）（2），[ n -Bu ₂ Sn（L ¹）] ₂ ·（C ₇ H ₈）（3），[Me ₂ Sn（L ³）] ₂·（C ₇ H ₈）（4），2 [ n -Bu ₂ Sn（L ³）] ₂ ·4（n -Bu ₂ Sn（L ³））（5），[Ph ₂ Sn（L ³）] （6），[Ph ₂ Sn（L ¹）]（7），[Ph ₂ Sn（L ⁴）]（8）和[Ph ₂ Sn（L ²）]（9）和结构特征。配体支架在配位的N和O原子之间的化学连接方面不同，该N或O原子是烷基或芳基部分。衍射结果表明，最小的甲基基团有利于通过Sn-O-Sn桥接和阳离子的六配位进行二聚。在这些双核衍生物中，亲核性较弱的酚盐O发现更多的不对称氧桥和更长的Sn⋯Sn分离。相反，庞大的苯基取代基阻止了两种配体的聚集，并始终导致五配位单核物种。所述Ñ -Bu基团在空间上更苛刻的比我但柔性的，从而导致中间行为。当O，N，O具有酚盐O的配体配位Sn（n- Bu）₂片段，发生临界情况，并且单核和双核复合物共存于同一结晶固体中。整体结构变化反映在一定范围的不同的艾迪生τ ₅ [艾迪生等人，J。化学式 道尔顿Trans。 1984年，1349-1356]描述了五重配位。为了更好的可比性我们引入一个稍微修改几何索引τ ' ₅，其中，所述基底角度α是由有机取代基所对着，而不管其绝对值。τ ' ₅代表关于Sn ^IV的配位几何的敏感指标。锡NMR结果表明，所有化合物均以单核五配位形式存在于溶液中。