Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstr 2, 37077, Göttingen, Germany.
Max-Planck-Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Mülheim an der Ruhr, Germany.
Angew Chem Int Ed Engl. 2017 Jul 17;56(30):8790-8794. doi: 10.1002/anie.201704185. Epub 2017 Jun 23.
A series of phosphines featuring a persistent radical were synthesized in two steps by condensation of dialkyl-/diarylchlorophosphines with stable cyclic (alkyl)(amino)carbenes (cAACs) followed by one-electron reduction of the corresponding cationic intermediates. Structural, spectroscopic, and computational data indicate that the spin density in these phosphines is mainly localized on the original carbene carbon from the cAAC fragment; thus, it remains in the α-position with respect to the central phosphorus atom. The potential of these α-radical phosphines to serve as spin-labeled ligands is demonstrated through the preparation of several Au derivatives, which were also structurally characterized by single-crystal X-ray diffraction.
一系列具有持久自由基的膦通过二烷基-/二芳基氯膦与稳定的环状（烷基）（氨基）卡宾（cAACs）缩合，然后对相应的阳离子中间体进行单电子还原两步合成。结构、光谱和计算数据表明，这些膦中的自旋密度主要定位于来自 cAAC 片段的原始卡宾碳上；因此，它相对于中心磷原子仍处于α-位。通过制备几种 Au 衍生物，证明了这些α-自由基膦作为自旋标记配体的潜力，这些衍生物也通过单晶 X 射线衍射进行了结构表征。
