Synthetic analogs for evaluating the influence of N-H•••S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase
Synthetic analogs for evaluating the influence of N-H•••S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase
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DOI：
10.1039/b901192g
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发表时间：
2009-01-01
影响因子：
4
通讯作者：
Riordan, Charles G.
中科院分区：
文献类型：
--
作者：
Ariyananda, Piyal W. G.;Kieber-Emmons, Matthew T.;Riordan, Charles G.
一系列方形平面甲基镍（II）配合物（dppe） Ni(Me)(SAr) （dppe = 1,2-二苯基膦乙烷）；2. Ar =苯基；3. Ar =五氟苯基；4. o-戊酰氨基苯基；5. Ar =对戊酰氨基苯基；（depe） Ni(Me)（SAr), （depe = 1,2-二乙基膦）乙烷）；7. Ar =苯基；8. Ar =五氟苯基；9. o-戊酰氨基苯基；10. 由（dppe）NiMe2(1)和（depe）NiMe2(6)与相应的硫醇或二硫化物反应合成了Ar = p-戊酰氨基苯基。这些配合物通过各种光谱方法进行了表征，包括P-31核磁共振、(HNMR)-H-1、C-13核磁共振和红外光谱，在大多数情况下通过x射线衍射分析。固态和溶液测量证实4和9含有分子内N-H中心点中心点S键。配合物2- 4,7 -10的羰基化通过酰基镍加合物（dRpe） Ni(C(O)Me)（SAr）的中间体（dRpe） Ni(CO)(2)和MeC(O) SAr，在低温下通过P-31核磁共振光谱检测到。密度泛函理论结果与实验观察结果一致，表明分子内氢键9与非氢键加合物相比，能稳定酰基镍加合物10。MeC(O)SC6F5对（dRpe）Ni（COD）的氧化加成，随后自发脱碳，产率变化，生成3和8。
A series of square planar methylnickel(II) complexes, (dppe) Ni(Me)(SAr) (dppe = 1,2-bis(diphenylphosphino) ethane); 2. Ar = phenyl; 3. Ar = pentafluorophenyl; 4. Ar = o-pivaloylaminophenyl; 5. Ar = p-pivaloylaminophenyl; (depe) Ni(Me)(SAr), (depe = 1,2-bis(diethylphosphino) ethane); 7. Ar = phenyl; 8. Ar = pentafluorophenyl; 9. Ar = o-pivaloylaminophenyl; 10. Ar = p-pivaloylaminophenyl), were synthesized via the reaction of (dppe)NiMe2 (1) and (depe)NiMe2 (6) with either the corresponding thiol or disulfide. These complexes were characterized by various spectroscopic methods including P-31 NMR, (HNMR)-H-1, C-13 NMR and infrared spectroscopies and in most cases by X-ray diffraction analyses. Solid state and solution measurements establish that 4 and 9 contain intramolecular N-H center dot center dot center dot S bonds. Carbonylation of the complexes 2-4, 7-10 leads to (dRpe) Ni(CO)(2) and MeC(O) SAr via the intermediacy of the acylnickel adducts, (dRpe) Ni(C(O)Me)(SAr), detected at low temperature by P-31 NMR spectroscopy. Consistent with experimental observations, density functional theory results reveal that the intramolecular hydrogen bond in 9 stabilizes the acylnickel adduct compared with its non-hydrogen-bonded adduct, 10. Oxidative addition of MeC(O)SC6F5 to (dRpe)Ni(COD) followed by spontaneous decarbonylation proceeds in variable yields generating 3 and 8.