Interactions of Cationic Palladium(
<scp>II</scp>
)‐ and Platinum(
<scp>II</scp>
)‐η
<sup>3</sup>
‐Allyl Complexes with Fluoride: Is Asymmetric Allylic Fluorination a Viable Reaction?
作者:Lukas Hintermann、Florian Läng、Pascal Maire、Antonio Togni
DOI:10.1002/ejic.200500795
日期:2006.4
The complex cations [M(η3-R2All)(PPFPz3-tBu})]+ (M = PdII, R2All = 1,3-diphenylallyl, 1,3-dicyclohexylallyl, indenyl; M = PtII, R2All = 1,3-diphenylallyl; PPFPz-3-tBu} = 3-tert-butyl-1-1-[2-diphenylphosphanyl-ferrocenyl]ethyl}-1H-pyrazole)have been prepared as salts with PF6– or SbF6–. They have been characterized by NMR spectroscopy in solution and by X-ray crystallography in the solid state. Their
复合阳离子 [M(η3-R2All)(PPFPz3-tBu})]+ (M = PdII, R2All = 1,3-二苯基烯丙基, 1,3-二环己基烯丙基, 茚基; M = PtII, R2All = 1,3 -二苯基烯丙基;PPFPz-3-tBu} = 3-叔丁基-1-1-[2-二苯基膦酰基-二茂铁基]乙基}-1H-吡唑)已与PF6-或SbF6-形成盐。它们已通过溶液中的 NMR 光谱和固态下的 X 射线晶体学进行表征。它们与亲核和“裸”氟化物源的反应已通过多核 NMR 光谱进行了研究。PdII 复合物没有经历任何亲核取代,伴随着烯丙基氟的释放。二环己基烯丙基片段通过消除以 1,3-二烯形式释放,但与其他烯丙基配合物的非特异性分解反应占主导地位。复合物 [Pt(η3-1, 3-Ph2C3H3)(PPFPz3-tBu})]PF6 与 Me4NF 进行阴离子交换得到 [Pt(1,3-P