Organozinc Fluoride and Trifluoromethyl Compounds Supported by the Bis(2-pyridylthio)methyl Ligand
Organozinc Fluoride and Trifluoromethyl Compounds Supported by the Bis(2-pyridylthio)methyl Ligand
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DOI：
10.1021/acs.organomet.2c00424
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发表时间：
2022-10
期刊：
影响因子：
2.8
通讯作者：
Daniel G. Shlian;G. Parkin
中科院分区：
文献类型：
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作者：
Daniel G. Shlian;G. Parkin
双（2-吡啶硫基）甲基配体[Bptm]已被用于合成{[Bptm]Zn（μ-F）}2，这是一种罕见的有机锌氟化物化合物。{[Bptm]Zn（μ-F）}2的二聚体性质具有不常见的[Zn（μ-F）] 2基序，与其他卤化物衍生物[Bptm]ZnX的单体结构形成对比（X = Cl，Br，I）;这种差异得到了密度泛函理论计算的支持，该计算表明氟化物衍生物倾向于具有桥连氟化物配体的二聚体形式，而其它衍生物则倾向于具有末端卤化物配体的单体结构。{[Bptm]Zn（μ-F）} 2与Me 3SiCF 3反应得到有机锌三氟甲基配合物[Bptm] ZnCF 3。该配合物中的Zn-CF 3键比先前报道的甲基衍生物[Bptm]ZnMe的Zn-CH 3键长，这一观察结果在相关锌化合物中是有先例的，但与其他金属配合物相反。对应于[Bptm] ZnCF 3的不对称C-F伸缩的红外频率对于金属三氟甲基物种是异常低的，但与其他锌和镉络合物的红外频率相当。
The bis(2-pyridylthio)methyl ligand, [Bptm], has been employed in the synthesis of {[Bptm]Zn(μ-F)}2, a rare example of an organozinc fluoride compound. The dimeric nature of {[Bptm]Zn(μ-F)}2, which possesses an uncommon [Zn(μ-F)]2motif, contrasts with the monomeric structures reported for the other halide derivatives, [Bptm]ZnX (X = Cl, Br, I); this difference is supported by density functional theory calculations which indicate that the fluoride derivative favors a dimeric form with bridging fluoride ligands, whereas the other derivatives favor monomeric structures with terminal halide ligands. {[Bptm]Zn(μ-F)}2reacts with Me3SiCF3to afford the organozinc trifluoromethyl complex, namely [Bptm]ZnCF3. The Zn–CF3bond in this complex is longer than the Zn–CH3bond of the previously reported methyl derivative [Bptm]ZnMe, an observation that is precedented in related zinc compounds but counter to other metal complexes. The infrared frequency corresponding to the asymmetric C–F stretch of [Bptm]ZnCF3is unusually low for a metal trifluoromethyl species but is comparable to those for other zinc and cadmium complexes.