Lanthanide Complexes Coordinated by a Dianionic Bis(amidinate) Ligand with a Rigid Naphthalene Linker
Lanthanide Complexes Coordinated by a Dianionic Bis(amidinate) Ligand with a Rigid Naphthalene Linker
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DOI：
10.1002/ejic.201000330
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发表时间：
2010-07
影响因子：
2.3
通讯作者：
M. Yakovenko;A. Cherkasov;G. Fukin;Dongmei Cui;A. Trifonov
中科院分区：
文献类型：
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作者：
M. Yakovenko;A. Cherkasov;G. Fukin;Dongmei Cui;A. Trifonov
详细阐述了一种新的具有刚性萘连接基的双脒配体1，8-C10 H6 [NHC-（tBu）=N（2，6-Me-2-C6 H3）][N=C（tBu）NH（2，6-Me-2-C6 H3）]（3）的合成途径。用两当量的nBuLi使该双（脒）配体去质子化，随后与无水LnCl反应（3）（Ln = Y，Nd，Sm）合成了[1，8-C10H6{NC（tBu）N-2，6-Me2C6H3}（2）]YCl（dme）（4），[1，8-C10H6{NC（tBu）N-2，6-Me（2）C6H（3）}（2）]Nd（dme）（mu-Cl）（2）Li（dme）（5），和[1，8-C10 H6 {NC（tBu）-N-2，6-Me-2-C6 H3}（2）]Sm（thf）（mu-Cl）（2）Li（thf）（2）（6），它们通过连接的双阴离子双（脒基）配体配位。配合物4-6的结构由X射线衍射研究确定，这表明新的配体框架可以根据中心原子离子的大小以不同的方式与镧系原子配位。配合物6与等摩尔量的LiCH 2SiMe 3的烷基化得到意外的酰胺基-脒基配合物[{1，8-C10 H6（NC（tBu）-N-2，6-Me-2-C6 H3）（2）}{1，8-C10 H6（NC（tBu）N-2，6-Me-2-C6 H3）-（NH）}Sm][Li（dme）（3）]（7），这显然是由于在瞬时烷基物质的分解和配体再分布期间一个脒基的裂解。
The synthetic pathway to a new bis(amidine) ligand with a conformationally rigid naphthalene linker, 1,8-C10H6[NHC-(tBu)=N(2,6-Me-2-C6H3)][N=C(tBu)NH(2,6-Me-2-C6H3)] (3) was elaborated. Deprotonation of this bis(amidine) ligand with two equivalents of nBuLi and subsequent reaction with anhydrous LnCl(3) (Ln = Y, Nd, Sm) allowed the synthesis of the chlorido complexes [1,8-C10H6{NC(tBu)N-2,6-Me2C6H3}(2)]YCl(dme) (4), [1,8-C10H6{NC(tBu)N-2,6-Me(2)C6H(3)}(2)]Nd(dme)(mu-Cl)(2)Li(dme) (5), and [1,8-C10H6{NC(tBu)-N-2,6-Me-2-C6H3}(2)]Sm(thf)(mu-Cl)(2)Li(thf)(2) (6), which are coordinated by the linked dianionic bis(amidinate) ligand. The structures of complexes 4-6 were established by X-ray diffraction studies, which reveal that the new ligand framework can coordinate to the lanthanide atoms in different fashions depending on the central atom ion size. Alkylation of complex 6 with equimolar amounts of LiCH2SiMe3 afforded the unexpected amido-amidinate complex [{1,8-C10H6(NC(tBu)-N-2,6-Me-2-C6H3)(2)}{1,8-C10H6(NC(tBu)N-2,6-Me-2-C6H3)-(NH)}Sm][Li(dme)(3)] (7), which obviously results from the cleavage of one amidinate group during decomposition of the transient alkyl species and ligand redistribution.