Abbenseth Josh, Delony Daniel, Neben Marc C, Würtele Christian, de Bruin Bas, Schneider Sven
Georg-August-Universität Göttingen, Institut für Anorganische Chemie, Tammannstraße 4, 37077, Göttingen, Germany.
Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam (UvA), Science Park 904, 1098, XH, Amsterdam, The Netherlands.
Angew Chem Int Ed Engl. 2019 May 6;58(19):6338-6341. doi: 10.1002/anie.201901470. Epub 2019 Apr 1.
The isolable complex [Os(PHMes*)H(PNP)] (Mes*=2,4,6- Bu C H ; PNP=N{CHCHP Bu } ) exhibits high phosphinyl radical character. This compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by P-H proton coupled electron transfer (PCET). The P-H bond dissociation energy (BDE) was determined by isothermal titration calorimetry and supporting DFT computations. The phosphinidene product exhibits electrophilic reactivity as demonstrated by intramolecular C-H activation.
可分离的配合物[Os(PHMes*)(H)(PNP)]（Mes* = 2,4,6 - Bu₃C₆H₂；PNP = N{CH₂CH₂PBu₂}₂）具有高膦酰基自由基特征。该化合物通过P-H质子耦合电子转移（PCET）可得到磷烯配合物[Os(PMes*)(H)(PNP)]。通过等温滴定量热法和辅助的密度泛函理论计算确定了P-H键解离能（BDE）。如分子内C-H活化所示，磷烯产物表现出亲电反应性。
