School of Chemistry, University of Bristol, Cantock's Close, Bristol, UK BS8 1TS.
Dalton Trans. 2010 Dec 7;39(45):10910-9. doi: 10.1039/c0dt00986e. Epub 2010 Oct 21.
A new series of sterically bulky, facially coordinating N(3)-donor tach-based ligands (tach; cis,cis-1,3,5-triaminocyclohexane) [2.1; cis,cis-1,3,5-tris(2,4-dimethylbenzylideneamino)cyclohexane, 4.1; cis,cis-1,3,5-tris(pentamethylbenzylideneamino)cyclohexane, 5.1; cis,cis-1,3,5-tris(2,6-dimethoxybenzylideneamino)cyclohexane, 6.1; cis,cis-1,3,5-tris(pentafluorobenzylideneamino)cyclohexane, 7.1; cis,cis-1,3,5-tris(3,5-bis(ditrifluoromethyl)benzylideneamino)cyclohexane, 8.1; cis,cis-1,3,5-tris(2-trifluoromethylbenzylideneamino)cyclohexane, 9.1; cis,cis-1,3,5-tris(2-methoxybenzylideneamino)cyclohexane] have been obtained from the condensation of tach with three equivalents of the appropriate substituted benzaldehyde. Reaction with [Cu(NCCH(3))(4)]PF(6) gives Cu(I) complexes of tach-based ligands {2.2-9.2, eg; 2.2; [Cu(2.1)(NCCH(3))]PF(6)}. Displacement of the acetonitrile ligand by CO was achieved successfully for all the Cu(I) complexes of tach-based ligands and the resulting complexes have been shown to bind carbon monoxide {2.3-9.3, eg; 2.3; [Cu(2.1)(CO)]PF(6)}. The X-ray single crystal structures of 5.1, 8.1, 9.1, 3.2, 7.2, 8.2, 9.2, 3.3, 5.3 and 6.3 have been determined.
已通过缩合反应，从顺式，顺式-1,3,5-三氨基环己烷（tach）与三个当量的合适取代苯甲醛，得到一系列新的空间位阻大、面配位的 N(3)-供体 tach 基配体[2.1；顺式，顺式-1,3,5-三（2,4-二甲基亚苄基氨基）环己烷，4.1；顺式，顺式-1,3,5-三（戊甲基亚苄基氨基）环己烷，5.1；顺式，顺式-1,3,5-三（2,6-二甲氧基亚苄基氨基）环己烷，6.1；顺式，顺式-1,3,5-三（五氟亚苄基氨基）环己烷，7.1；顺式，顺式-1,3,5-三（3,5-二（三氟甲基）亚苄基氨基）环己烷，8.1；顺式，顺式-1,3,5-三（2-三氟甲基亚苄基氨基）环己烷，9.1；顺式，顺式-1,3,5-三（2-甲氧基亚苄基氨基）环己烷]。与 [Cu(NCCH(3))(4)]PF(6)反应，得到 tach 基配体的 Cu(I)配合物{2.2-9.2，例如；2.2；[Cu(2.1)(NCCH(3))]PF(6)}。所有 tach 基配体的 Cu(I)配合物均成功地将乙腈配体取代为 CO，所得配合物已被证明能结合一氧化碳{2.3-9.3，例如；2.3；[Cu(2.1)(CO)]PF(6)}。已确定 5.1、8.1、9.1、3.2、7.2、8.2、9.2、3.3、5.3 和 6.3 的 X 射线单晶结构。
