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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and structural characterisation of new organo-diimido tantalum and niobium complexes
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Synthesis and structural characterisation of new organo-diimido tantalum and niobium complexes

机译：新型有机二亚胺基钽和铌配合物的合成与结构表征

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摘要

The organo-diimido tantalum complexes [{Ta(L_2)Cl_3}_2(mu-l,n-NC_6H_4N)],L=MeCN (1) and 4-~tBupy (2),have been prepared by two alternative experimental methods: (1) the initial formation of the corresponding TaCl_4centre dotL adduct,L=4-~tBupy or CH_3CN,followed by addition of the appropriate phenylenediamine,or (2) the initial formation of the corresponding organo-diimido species and subsequent addition of the ligand L.These complexes,as well as some related niobium complexes,were alkylated using the appropriate Grignard reagent to afford the alkyl-containing complexes [{M(L)R_3}_2(mu-l,n-NC_6H_4N)] (4,5,6,7,8,9) (M=Nb,Ta: n=3,4;L=MeCN,R=CH_2SiMe_3,CH_2CMe_3,CH_2CMe_2Ph).These complexes can be prepared by treating the corresponding chloro-complexes with dialkyl-magnesium reagents MgR_2(THF)_2.Niobium complexes containing THF ligands,i.e.[{Nb(THF)R_3}_2(mu-l,3-NC_6-H_4N)] (10,11) (R=CH_2SiMe_3,CH_2CMe_3),were isolated by using THF as the solvent and also from the acetonitrile-containing complexes 8b and 9b by simply adding THF.The complex [{Nb(CH_2CMe_2Ph)_3}_2(mu-l,4-NC_6H_4N)] (12a) was prepared by addition of the corresponding Grignard reagent to a suspension of [{Nb(MeCN)_2Cl_3}_2(mu-l,4-NC_6-H_4N)] in THF.The reaction of complexes [{M(MeCN)_2Cl_3}_2(mu-l,n-NC_6H_4N)] (M=Ta,Nb;n=3,4) with Li[C_5H_4-SiMe_3] was carried out and afforded the tetrakis-cyclopentadienyl-diimido complexes [{M(eta~5-C_5H_4SiMe_3)_2Cl}_2-(mu-l,n-NC_6H_4N)] [M=Ta,n=4 (13a);M=Ta,n=3 (13b);M=Nb,n=4 (14a);M=Nb,n=3 (14b)].The structure of 13a has been solved by X-ray diffraction.Finally,we have performed the reactions between the diimido-containing compounds [{M(MeCN)_2Cl_3}_2(mu-l,n-NC_6H_4N)] (M=Ta,Nb;n=3,4) and the lithium benzamidinate Li[PhC-(NSiMe_3)_2] to afford the benzamidinate-containing complexes [{M[PhC(NSiMe_3)_2]_2Cl}_2(mu-l,n-NC_6H_4N)] [M=Ta,n=4 (15a);M=Ta,n-3 (15b);M=Nb,n=4 (16a)].The structures of the different families of compounds were determined by spectroscopic methods.
机译：有机二亚胺基钽配合物[{Ta（L_2）Cl_3} _2（mu-1，n-NC_6H_4N）]，L = MeCN（1）和4-tBupy（2），已通过两种替代实验方法制备： （1）初始形成相应的TaCl_4中心点L加合物，L = 4-tBupy或CH_3CN，随后加入适当的苯二胺，或（2）初始形成相应的有机二亚胺基物种，然后加入配体L.使用适当的格利雅试剂将这些配合物以及一些相关的铌配合物烷基化，得到含烷基的配合物[{M（L）R_3} _2（mu-1，n-NC_6H_4N）]（4,5 ，6,7,8,9）（M = Nb，Ta：n = 3,4; L = MeCN，R = CH_2SiMe_3，CH_2CMe_3，CH_2CMe_2Ph）这些配合物可以通过用二烷基-镁试剂MgR_2（THF）_2。含有[{Nb（THF）R_3} _2（mu-1,3-NC_6-H_4N）]（10,11）（R = CH_2SiMe_3，CH_2CMe_3）的铌配合物通过使用THF作为溶剂和乙腈-容器素分离通过简单地添加THF，得到8g和8b的配合物。通过将相应的格氏试剂添加到[{Nb （MeCN）_2Cl_3} _2（mu-1,4-NC_6-H_4N）]。配合物[{M（MeCN）_2Cl_3} _2（mu-1，n-NC_6H_4N）]的反应（M = Ta，Nb ; n = 3,4）与Li [C_5H_4-SiMe_3]进行反应，得到四-环戊二烯基-二亚氨基配合物[{M（eta〜5-C_5H_4SiMe_3）_2Cl} _2-（mu-1，n-NC_6H_4N）] [M ＝ Ta，n ＝ 4（13a）; M ＝ Ta，n ＝ 3（13b）; M ＝ Nb，n ＝ 4（14a）; M ＝ Nb，n ＝ 3（14b）]。13a的结构最后，我们进行了含二亚氨基化合物[{M（MeCN）_2Cl_3} _2（mu-1，n-NC_6H_4N）]之间的反应（M = Ta，Nb; n = 3,4）和苯甲酰胺酸锂Li [PhC-（NSiMe_3）_2]得到含苯甲酰胺酸的络合物[{M [PhC（NSiMe_3）_2] _2Cl} _2（mu-1，n-NC_6H_4N）] [M = Ta，n = 4（15a）; M = Ta，n-3（15b）; M = Nb，n = 4（16a）]。采用光谱法测定了不同族化合物的结构。

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