Aluminium Complexes of a Sterically Demanding Bis(iminophosphorane)methandiide
Aluminium Complexes of a Sterically Demanding Bis(iminophosphorane)methandiide
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空间要求高的双(亚氨基正膦)二甲基化物的铝配合物
DOI：
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发表时间：
2013
期刊：
影响因子：
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通讯作者：
A. Stasch
中科院分区：
文献类型：
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作者：
Christian P. Sindlinger;A. Stasch
在不同条件下，要求空间位阻的双（亚氨基膦）甲烷{DipN=P（Ph 2）} 2CH 2，H2 L1（其中Dip = 2，6-iPr 2C 6 H3）与1或2当量的AlMe 3在甲苯中的反应分别导致甲烷化物络合物[HLAlMe 2] 4和甲烷二化物络合物[L（AlMe 2）2] 5。配合物5与I2在甲苯中的迭代碘化产生配合物[L（AlMeI）2] 6和[L（AlI 2）2] 7。对配合物4-7进行了结构表征。甲烷化物4形成了一个没有Al-C（甲烷化物）接触的褶皱六元环，配合物5和6显示甲烷二化物配体与两个Al原子配位，在中心螺环碳中心上形成两个四元环。配合物7在固态下表现出两个Al中心与甲烷二化物配体的不对称配位模式，具有几乎平面的、严重扭曲的三配位甲烷二化物碳原子和只有一个短的Al-C键。
The reaction of the sterically demanding bis(iminophosphorane)methane, {DipN=P(Ph2)}2CH2, H2L 1 (where Dip = 2,6-iPr2C6H3), with one or two equivalents of AlMe3 in toluene under varying conditions led to the methanide complex [HLAlMe2] 4, and the methandiide complex [L(AlMe2)2] 5, respectively. Iterative iodination of complex 5 with I2 in toluene yielded the complexes [L(AlMeI)2] 6 and [L(AlI2)2] 7. The complexes 4–7 were structurally characterised. The methanide 4 forms a puckered six-membered ring without Al-C(methanide) contact and the complexes 5 and 6 show coordination of the methandiide ligand to two Al atoms forming two four-membered rings on the central spirocyclic carbon centre. Complex 7 shows an asymmetric coordination mode of the two Al centres to the methandiide ligand in the solid state with an almost planar, severely distorted three-coordinate methandiide carbon atom and only one short Al–C bond.