Department of Chemistry, 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2013 Oct 16;135(41):15338-41. doi: 10.1021/ja408964g. Epub 2013 Oct 3.
A substituted TREN has been prepared in which the aryl groups in (ArylNHCH2CH2)3N are substituted at the 3- and 5-positions with a total of six OCH2(CH2)nCH═CH2 groups (n = 1, 2, 3). Molybdenum nitride complexes, [(ArylNCH2CH2)3N]Mo(N), have been isolated as adducts that contain B(C6F5)3 bound to the nitride. Two of these [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) complexes (n = 1 and 3) were crystallographically characterized. After removal of the borane from [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) with PMe3, ring-closing olefin metathesis (RCM) was employed to join the aryl rings with OCH2(CH2)nCH═CH(CH2)nCH2O links (n = 1-3) between them. RCM worked best with a W(O)(CHCMe3)(Me2Pyr)(OHMT)(PMe2Ph) catalyst (OHMT = hexamethylterphenoxide, Me2Pyr = 2,5-dimethylpyrrolide) and n = 3. The macrocyclic ligand was removed from the metal through hydrolysis and isolated in 70-75% yields relative to the borane adducts. Crystallographic characterization showed that the macrocyclic TREN ligand in which n = 3 contains three cis double bonds. Hydrogenation produced a TREN in which the three links are saturated, i.e., O(CH2)10O.
已制备出一种取代的 TREN，其中（ArylNHCH2CH2）3N 中的芳基在 3-和 5-位被总共六个 OCH2(CH2)nCH═CH2 基团取代（n = 1、2、3）。已经分离出作为加合物的含 Mo(N)的氮化钼配合物，其中含有与氮化物结合的 B(C6F5)3。这些 [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) 配合物中的两个（n = 1 和 3）通过晶体学进行了表征。用 PMe3 从 [(ArylNCH2CH2)3N]Mo(NB(C6F5)3) 中除去硼烷后，采用闭环烯烃复分解（RCM）将芳环与 OCH2(CH2)nCH═CH(CH2)nCH2O 键（n = 1-3）连接起来。带有 W(O)(CHCMe3)(Me2Pyr)(OHMT)(PMe2Ph) 催化剂（OHMT = 六甲基三苯氧化物，Me2Pyr = 2,5-二甲基吡咯烷）和 n = 3 的情况下，RCM 效果最佳。通过水解将大环配体从金属中除去，并以相对于硼烷加合物 70-75%的收率分离出来。晶体学表征表明，n = 3 的大环 TREN 配体含有三个顺式双键。氢化产生了一种 TREN，其中三个键均饱和，即 O(CH2)10O。
