Ambidentate Thiocyanate and Cyanate Ligands in Dinitrosyl Iron Complexes
學年 101
學期 2
出版（發表）日期 2013-02-01
作品名稱 Ambidentate Thiocyanate and Cyanate Ligands in Dinitrosyl Iron Complexes
作品名稱（其他語言）
著者 Hsieh, Chung-Hung; Brothers, Scott M.; Reibenspies, Joseph H.; Hall, Michael B.; Popescu, Codrina V.; Darensbourg, Marcetta Y.
單位 淡江大學化學學系
出版者 Washington, DC: American Chemical Society
著錄名稱、卷期、頁數 Inorganic Chemistry 52(4), pp.2119-2124
摘要 To explore the effect of delocalization in the Fe(NO)2 unit on possible linkage isomerism of ambidentate ECN– ligands, E = S and O, anionic DNICs, dinitrosyl iron complexes, (SCN)2Fe(NO)2– (1) and (OCN)2Fe(NO)2– (2) were synthesized by the reaction of in situ-generated [Fe(CO)2(NO)2]+ and PPN+ECN–. Other {Fe(NO)2}9 (Enemark–Feltham notation) complexes, (N3)2Fe(NO)2– and (PhS)2Fe(NO)2–, were prepared for comparison. The X-ray diffraction analysis of 1 and 2 yielded the typical tetrahedral structures of DNICs with two slightly bent Fe–N–O oriented toward each other, and linear FeNCE units. The ν(NO) IR values shift to lower values for 1 > 2 > (N3)2Fe(NO)2– > (PhS)2Fe(NO)2–, reflecting the increasing donor ability of the ancillary ligands and consistent with the redox potentials of the complexes, and the small trends in Mössbauer isomer shifts. Computational studies corroborate that the {Fe(NO)2}9 motif prefers N-bound rather than E-bound isomers. The calculated energy differences between the linkage isomers of 1 (Fe-NCS preferred over Fe-SCN by about 6 kcal/mol) are smaller than those of 2 (Fe-NCO preferred over Fe-OCN by about 16 kcal/mol), a difference that is justified by the frontier molecular orbitals of the ligands themselves.
關鍵字
語言 en_US
ISSN 1520-510X
期刊性質 國外
收錄於 SCI
產學合作
通訊作者
審稿制度 是
國別 USA
公開徵稿
出版型式 ,電子版,紙本
相關連結

機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/97537 )

機構典藏連結