Syntheses and structural analyses of chiral rhenium containing amines of the formula (η5-C5H5)Re(NO)(PPh3)((CH2)nNRR′) (n=0, 1)
Syntheses and structural analyses of chiral rhenium containing amines of the formula (η5-C5H5)Re(NO)(PPh3)((CH2)nNRR′) (n=0, 1)
复制标题
含胺手性铼的合成和结构分析 (η5-C5H5)Re(NO)(PPh3)((CH2)nNRRâ²) (n=0, 1)
DOI：
10.1016/j.ica.2009.03.047
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发表时间：
2010
影响因子：
2.8
通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
--
作者：
Seidel, Sabine N.;Prommesberger, Markus;Eichenseher, Sandra;Meyer, Oliver;Hampel, Frank;Gladysz, John A.
外消旋甲基配合物（η5-C5 H5）Re（NO）（PPh 3）（CH 3）（1）先与CF 3SO 3 H反应，再与NH 2CH 2C 6 H5反应，得到[（η5-C5 H5）Re（NO）（PPh 3）（NH 2CH 2C 6 H5）]+ CF 3SO 3-（[4a-H]+ CF 3SO 3-; 73%），再与t-BuOK脱质子，得到酰胺配合物（η5-C5 H5）Re（NO）（PPh 3）（NHCH 2C 6 H5）（76%）。1与Ph 3C +X−反应，然后与伯胺或仲胺反应，得到[（η5-C5 H5）Re（NO）（PPh 3）]（CH2NHRR′）]+X−（[6-H]+X−; R/R′/X=a，H/NH2CH2C6H5/BF4; a′，H/NH2CH2C6H5/PF6; B，H/NH2CH2（CH2）2CH3/PF6; c，H/（S）-NH2CH（CH3）C6H5/BF4）; d，CH2CH3/CH2CH3/PF6; e，CH2（CH2）2CH3/CH2（CH2）2CH3/PF6; f，CH2C6H5/CH2C6H5/PF6; g，-CH2（CH2）2CH2-/PF6; h，-CH2（CH2）3CH2-/PF6; i，CH3/CH2CH2OH/PF6（62-99%）。用t-BuOK去质子化得到胺（η5-C5 H5）Re（NO）（PPh 3）（CH 2NRR ′）（6a-i; 99-40%），当R = H时，其更稳定且以分析纯形式分离。对映体纯1用于制备（RReSC）-[6c-H]+ BF 4-、（RReSC）-6c、（S）-[6 g-H]+ PF 6-和（S）-6g。测定了[4a-H]+ CF_3SO_3 ~-、[6a′，d，f，h-H]+ PF_6 ~-、（RReSC）_6c和6 f的晶体结构，并对其进行了详细的分析，特别是对阳离子/阴离子氢键和构象进行了详细的研究。与类似的含膦的环氧化物相比，6a_i在由有机胺催化的反应中显示出差的活性。
The reaction of the racemic chiral methyl complex (η5-C5H5)Re(NO)(PPh3)(CH3) (1) with CF3SO3H and then NH2CH2C6H5gives [(η5-C5H5)Re(NO)(PPh3)(NH2CH2C6H5)]+CF3SO3- ([4a-H]+CF3SO3-; 73%), and deprotonation with t-BuOK affords the amido complex (η5-C5H5)Re(NO)(PPh3)(NHCH2C6H5) (76%). Reactions of 1 with Ph3C+X−and then primary or secondary amines give [(η5-C5H5)Re(NO)(PPh3)(CH2NHRR′)]+X−([6-H]+X−; R/R′/X=a, H/NH2CH2C6H5/BF4; a′, H/NH2CH2C6H5/PF6; b, H/NH2CH2(CH2)2CH3/PF6; c, H/(S)-NH2CH(CH3)C6H5/BF4); d, CH2CH3/CH2CH3/PF6; e, CH2(CH2)2CH3/CH2(CH2)2CH3/PF6; f, CH2C6H5/CH2C6H5/PF6; g, -CH2(CH2)2CH2-/PF6; h, –CH2(CH2)3CH2–/PF6; i, CH3/CH2CH2OH/PF6(62–99%). Deprotonations with t-BuOK afford the amines (η5-C5H5)Re(NO)(PPh3)(CH2NRR′) (6a–i; 99–40%), which are more stable and isolated in analytically pure form when R≠H. Enantiopure 1 is used to prepare (RReSC)-[6c-H]+BF4-, (RReSC)-6c, (S)-[6g-H]+PF6-, and (S)-6g. The crystal structures of [4a-H]+CF3SO3-, a previously prepared NH2CH2Si(CH3)3analog, [6a′,d,f,h-H]+PF6-, (RReSC)-6c, and 6f are determined and analyzed in detail, particularly with respect to cation/anion hydrogen bonding and conformation. In contrast to analogous rhenium containing phosphines, 6a–i show poor activities in reactions that are catalyzed by organic amines.