Department of Chemistry, University of Toronto, 80 St George St, Toronto, Ontario, Canada M5S3H6.
Dalton Trans. 2012 Feb 21;41(7):2131-9. doi: 10.1039/c1dt11820j. Epub 2011 Dec 20.
The lutidine derivative (2,6-Me(2))(4-Bpin)C(5)H(2)N when combined with B(C(6)F(5))(3) yields a frustrated Lewis pair (FLP) which reacts with H(2) to give the salt [(2,6-Me(2))(4-Bpin)C(5)H(2)NH][HB(C(6)F(5))(3)] (1). Similarly 2,2'-(C(5)H(2)(4,6-Me(2))N)(2) and (4,4'-(C(5)H(2)(4,6-Me(2))N)(2) were also combined with B(C(6)F(5))(3) and exposed to H(2) to give [(2,2'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(4,6-Me(2))N][HB(C(6)F(5))(3)] (2) and [(4,4'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))N] [HB(C(6)F(5))(3)] (3), respectively. The mono-pyridine-N-oxide 4,4'-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO formed the adduct (4,4'-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)(B(C(6)F(5))(3)) (4) which reacts further with B(C(6)F(5))(3) and H(2) to give [(4,4'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)B(C(6)F(5))(3)] [HB(C(6)F(5))(3)] (5). In a related sense, 2-amino-6-CF(3)-C(5)H(3)N reacts with B(C(6)F(5))(3) to give (C(5)H(3)(6-CF(3))NH)(2-NH(B(C(6)F(5))(3))) (6). Similarly, the species, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine were reacted with B(C(6)F(5))(3) to give the products as (C(9)H(6)NH)(2-NHB(C(6)F(5))(3)) (7), (C(9)H(6)N)(8-NH(2)B(C(6)F(5))(3)) (8) and (C(5)H(3)(6-Me)NH)(2-OB(C(6)F(5))(3)) (9), respectively; while 2-amino-6-picoline, 2-amino-6-CF(3)-pyridine, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine react with ClB(C(6)F(5))(2) to give the species (C(5)H(3)(6-R)NH)(2-NH(ClB(C(6)F(5))(2))) (R = Me (10), R = CF(3) (11)) (C(9)H(6)NH)(2-NH(ClB(C(6)F(5))(2))) (12), (C(9)H(6)N)(8-NH(2)ClB(C(6)F(5))(2)) (13) and (C(5)H(3)(6-Me)NH)(2-OClB(C(6)F(5))(2)) (14), respectively. In a similar manner, 2-amino-6-picoline and 2-amino-quinoline react with B(C(6)F(5))(2)H to give (C(5)H(3)(6-Me)NH)(2-NH(HB(C(6)F(5))(2))) (15) and (C(9)H(6)NH)(2-NH(HB(C(6)F(5))(2))) (16). The corresponding reaction of 8-amino-quinoline yields (C(9)H(6)N)(8-NHB(C(6)F(5))(2)) (17). In a similar fashion, reaction of 2-amino-6-CF(3)-pyridine resulted in the formation of (18) formulated as (C(5)H(3)(6-CF(3))N)(2-NH(B(C(6)F(5))(2)). Finally, treatment of 15 with iPrMgCl gave (C(9)H(6)N)(2-NH(B(C(6)F(5))(2))) (19). Crystallographic studies of 1, 2, 4, 6, 7, 10, 11, 12 and 15 are reported.
当 2,6-Me(2))(4-Bpin)C(5)H(2)N 与 B(C(6)F(5))(3) 结合时，会产生一个受阻路易斯对 (FLP)，它与 H(2) 反应生成盐 [(2,6-Me(2))(4-Bpin)C(5)H(2)NH][HB(C(6)F(5))(3)] (1)。同样地，2,2'-(C(5)H(2)(4,6-Me(2))N)(2) 和 (4,4'-(C(5)H(2)(4,6-Me(2))N)(2) 也与 B(C(6)F(5))(3) 结合并暴露于 H(2)，生成 [(2,2'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(4,6-Me(2))N][HB(C(6)F(5))(3)] (2) 和 [(4,4'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))N][HB(C(6)F(5))(3)] (3)。单吡啶-N-氧化物 4,4'-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO 形成加合物 (4,4'-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)(B(C(6)F(5))(3)) (4)，它进一步与 B(C(6)F(5))(3) 和 H(2) 反应，生成 [(4,4'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)B(C(6)F(5))(3)] [HB(C(6)F(5))(3)] (5)。在类似的情况下，2-氨基-6-CF(3)-C(5)H(3)N 与 B(C(6)F(5))(3) 反应生成 (C(5)H(3)(6-CF(3))NH)(2-NH(B(C(6)F(5))(3))) (6)。同样，2-氨基喹啉、8-氨基喹啉和 2-羟基-6-甲基吡啶与 B(C(6)F(5))(3) 反应生成产物 (C(9)H(6)NH)(2-NHB(C(6)F(5))(3)) (7)、(C(9)H(6)N)(8-NH(2)B(C(6)F(5))(3)) (8) 和 (C(5)H(3)(6-Me)NH)(2-OB(C(6)F(5))(3)) (9)，而 2-氨基-6-吡啶、2-氨基-6-CF(3)-吡啶、2-氨基喹啉、8-氨基喹啉和 2-羟基-6-甲基吡啶与 ClB(C(6)F(5))(2) 反应生成 (C(5)H(3)(6-R)NH)(2-NH(ClB(C(6)F(5))(2))) (R = Me (10)，R = CF(3) (11))、(C(9)H(6)NH)(2-NH(ClB(C(6)F(5))(2))) (12)、(C(9)H(6)N)(8-NH(2)ClB(C(6)F(5))(2)) (13) 和 (C(5)H(3)(6-Me)NH)(2-OClB(C(6)F(5))(2)) (14)。同样地，2-氨基-6-吡啶和 2-氨基喹啉与 B(C(6)F(5))(2)H 反应生成 (C(5)H(3)(6-Me)NH)(2-NH(HB(C(6)F(5))(2))) (15) 和 (C(9)H(6)NH)(2-NH(HB(C(6)F(5))(2))) (16)。8-氨基喹啉的相应反应生成 (C(9)H(6)N)(8-NHB(C(6)F(5))(2)) (17)。以类似的方式，2-氨基-6-CF(3)-吡啶的反应生成 (C(5)H(3)(6-CF(3))N)(2-NH(B(C(6)F(5))(2))) (18)。最后，用 iPrMgCl 处理 15 得到 (C(9)H(6)N)(2-NH(B(C(6)F(5))(2))) (19)。报道了 1、2、4、6、7、10、11、12 和 15 的晶体结构研究。
