亲核钯卡宾的氧化反应：单自由基卡宾和双自由基卡宾
Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes.
作者信息
Cui Peng, Hoffbauer Melissa R, Vyushkova Mariya, Iluc Vlad M
机构信息
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA.
出版信息
Dalton Trans. 2019 Jul 2;48(26):9663-9668. doi: 10.1039/c9dt00585d.
Palladium(ii) cationic carbene radical and neutral bi-radical complexes were synthesized from a previously reported Pd(ii) carbene in the presence of one and two electron oxidants. When [{PC(sp2)P}tBuPd(PMe3)] (1, [PC(sp2)P]tBu = (bis[2-(di-iso-propylphosphino)-4-tertbutylphenyl]methylene)) was treated with [Cp2Fe][X] (X = BArF4, ArF = 3,5-(CF3)2C6H3, or PF6), the corresponding radical cationic complexes [{PC˙(sp2)P}tBuPd(PMe3)][X] (2: X = BArF4, 3: PF6) were isolated and characterized. Magnetic moment measurements and EPR spectroscopy indicated the presence of a ligand centered unpaired electron. In the presence of two electron oxidants such as 1,8-naphthylene disulfide or 9,10-anthracenedione, 1 converts to [{PC˙(sp2)P}tBuPdS(C10H6)SPd{PC˙(sp2)P}tBu] (4) or [{PC˙(sp2)P}tBuPdO(C14H10)OPd{PC˙(sp2)P}tBu] (5), respectively. Single crystal X-ray diffraction and EPR spectroscopy confirmed the bi-radical nature of 4 and 5.
钯（II）阳离子卡宾自由基和中性双自由基配合物是由先前报道的钯（II）卡宾在一电子和二电子氧化剂存在下合成的。当用[Cp2Fe][X]（X = BArF4，ArF = 3,5-(CF3)2C6H3，或PF6）处理[{PC(sp2)P}tBuPd(PMe3)]（1，[PC(sp2)P]tBu = （双[2-(二异丙基膦基)-4-叔丁基苯基]亚甲基））时，分离并表征了相应的自由基阳离子配合物[{PC˙(sp2)P}tBuPd(PMe3)][X]（2：X = BArF4，3：PF6）。磁矩测量和电子顺磁共振光谱表明存在以配体为中心的未成对电子。在1,8-萘二硫化物或9,10-蒽二酮等二电子氧化剂存在下，1分别转化为[{PC˙(sp2)P}tBuPdS(C10H6)SPd{PC˙(sp2)P}tBu]（4）或[{PC˙(sp2)P}tBuPdO(C14H10)OPd{PC˙(sp2)P}tBu]（5）。单晶X射线衍射和电子顺磁共振光谱证实了4和5的双自由基性质。
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