Synthesis of triamidoamine ligands of the type (ArylNHCH2CH2)3N and molybdenum and tungsten complexes that contain an [(ArylNCH2CH2)3N]3- ligand
Synthesis of triamidoamine ligands of the type (ArylNHCH2CH2)3N and molybdenum and tungsten complexes that contain an [(ArylNCH2CH2)3N]3- ligand
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DOI：
10.1021/ic001122v
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发表时间：
2001-07-30
影响因子：
4.6
通讯作者：
Schrock, RR
中科院分区：
文献类型：
--
作者：
Greco, GE;Schrock, RR
芳基溴化物与(H2NCH2CH2)(3)N在Pd-2(Dba)(3)催化下在BINAP和NaO-t-Bu的催化下反应生成芳基衍生物(芳基NHCH(2)CH(2))3N[芳基=C6H5(1a)，4-FC6H4(1b)，4-t-BuC6H4(1c)，3，5-Me2C6H3(1d)，3，5-Ph2C6H3(1e)，3，5-(4-t-BuC6H4)(2)C6H3(1f)，2-Me6C6H4(1g)，2，4，6-Me3C6H2(1h)]。(ArNHCH2CH2)(3)N(Ar=C6H5，4-FC6H4，3，5-Me2C6H3，3，5-Ph2C6H3)与Mo(NMe2)(4)在甲苯中70℃反应生成[(ArNHCH2CH2)(3)N]Mo(NMe2)，产率从到96%。二甲胺类化合物(Ar=4-FC6H4，3，5-Me2C6H3)在四氢呋喃(THF)中与2，6-二氢呋喃反应可转化为顺磁性的[(ArNHCH2CH2)(3)N]-MoCl型化合物。在四氢呋喃中，1a-f与MoCl4(THF)(2)“直接反应”，然后与3当量的MeMgCl反应，高产率地生成[(ArNHCH_2CH_2)(3)N]MoCl物种(3a-f)。如果直接反应中用4当量的石灰代替MeMgCl，则生成[(ArNHCH_2CH_2)(3)N]多金属物种。钨物种[(ArNHCH_2CH_2)(3)N]WCL可以用类似的“直接”方法制备。循环伏安研究表明，随着[(ArNHCH_2CH2)(3)N](3-)配体给电子能力的增加，MoCl络合物的还原变得更加困难，并且还原变得不可逆，与氯从{[(ArNHCH_2CH2)(3)N]MoCl}(-)容易损失一致。钨络合物更难还原，而且还原在循环伏安时间尺度上是不可逆的。
Aryl bromides react with (H2NCH2CH2)(3)N in a reaction catalyzed by Pd-2(dba)(3) in the presence of BINAP and NaO-t-Bu to give the arylated derivatives (ArylNHCH(2)CH(2))3N [Aryl = C6H5 (1a), 4-FC6H4 (1b), 4-t-BuC6H4 (1c), 3,5-Me2C6H3 (1d), 3,5-Ph2C6H3 (1e), 3,5-(4-t-BuC6H4)(2)C6H3 (1f), 2-MeC6H4 (1g), 2,4,6-Me3C6H2 (1h)]. Reactions between (ArNHCH2CH2)(3)N (Ar = C6H5, 4-FC6H4, 3,5-Me2C6H3, and 3,5-Ph2C6H3) and Mo(NMe2)(4) in toluene at 70 degreesC lead to [(ArNHCH2CH2)(3)N]Mo(NMe2) complexes in yields ranging from 64 to 96%. Dimethylamido species (Ar = 4-FC6H4, 3,5-Me2C6H3) could be converted into paramagnetic [(ArNHCH2CH2)(3)N]-MoCl species by treating them with 2,6-lutidinium chloride in tetrahydrofuran (THF). The "direct reaction" between 1a-f and MoCl4(THF)(2) in THF followed by 3 equiv of MeMgCl yielded [(ArNHCH2CH2)(3)N]MoCl species (3a-f) in high yield. If 4 equiv of LiMe instead of MeMgCl are employed in the direct reaction, then [(ArNHCH2CH2)(3)N]MoMe species are formed. Tungsten species, [(ArNHCH2CH2)(3)N]WCl, could be prepared by analogous "direct" methods. Cyclic voltammetric studies reveal that MoCl complexes become more difficult to reduce as the electron donating ability of the [(ArNHCH2CH2)(3)N](3-) ligand increases, and the reductions become less reversible, consistent with ready loss of chloride from {[(ArNHCH2CH2)(3)N]MoCl}(-). Tungsten complexes are more difficult to reduce, and reductions are irreversible on the CV time scale.