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Trimethylsilyldiazomethane Disassembly at a Three-Fold Symmetric Iron Site
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-05-23 , DOI: 10.1021/acs.inorgchem.4c00604
Austin D Chivington 1 , Sammie Squire 1 , Nobuyuki Yamamoto 1 , Maren Pink 1 , Morgan D Griffith 2, 3 , Jess Fletcher 3 , Yafei Gao 1 , Joseph M Zadrozny 2, 3 , Jeremy M Smith 1
Affiliation  

The reaction of equimolar trimethylsilyldiazomethyllithium (LiTMSD) with high spin (S = 2) PhB(AdIm)3FeCl (PhB(AdIm)3 = tris(3-adamantylimidazol-2-ylidene)phenylborate) affords the corresponding N-nitrilimido complex PhB(AdIm)3Fe–N═N═C(SiMe3). This complex can be converted to the thermodynamically more favorable C-isocyanoamido isomer PhB(AdIm)3Fe–C═N═N(SiMe3) by reaction with an additional equivalent of LiTMSD. While the iron(II) complexes are four-coordinate, the diazomethane is bound side-on in the iron(I) congener PhB(AdIm)3Fe(N,N′-κ2-N2C(H)Si(CH3)3). The latter complex adopts high spin (S = 3/2) ground state and features an unusually weak C–H bond. Photolysis of the iron(II) complexes induces N═N bond cleavage, with the iron(II) cyanide PhB(AdIm)3Fe–C≡N and iron(IV) nitride PhB(AdIm)3Fe≡N complexes being the major products of the reaction. The same products are obtained when the iron(I) complex is photolyzed or treated with a fluoride source. The trimethylsilyldiazomethane-derived ligand disassembly reactions are contrasted with those observed for related tris(carbene)amine complexes.

中文翻译:


三重对称铁位点的三甲基甲硅烷基重氮甲烷分解



等摩尔三甲基硅基重氮甲基锂 (LiTMSD) 与高自旋 ( S = 2) PhB(AdIm) 3 FeCl (PhB(AdIm) 3 = 三(3-金刚烷基咪唑-2-亚基)苯基硼酸盐) 的反应得到相应的N-氮基亚胺络合物 PhB (AdIm) 3 Fe–N=N=C(SiMe 3 )。通过与额外当量的LiTMSD反应,该配合物可以转化为热力学上更有利的C-异氰基酰胺异构体PhB(AdIm) 3 Fe–C=N=N(SiMe 3 )。虽然铁 (II) 配合物是四配位的,但重氮甲烷在铁 (I) 同系物 PhB(AdIm) 3 Fe( N , N '-κ 2 -N 2 C(H)Si(CH) 中侧键结合33 )。后者配合物采用高自旋( S =3/2)基态,并具有异常弱的C-H键。铁(II)配合物的光解会引起N=N键断裂,其中氰化铁(II) PhB(AdIm) 3 Fe–CeqN和氮化铁(IV) PhB(AdIm) 3 FeeqN配合物是主要的配合物反应的产物。当铁(I)络合物被光解或用氟化物源处理时,可以获得相同的产物。三甲基甲硅烷基重氮甲烷衍生的配体分解反应与相关三(卡宾)胺配合物中观察到的反应形成对比。
更新日期:2024-05-23
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