Fischbach Urs, Trincado M, Grützmacher Hansjörg
Cilag AG, 8200 Schaffhausen, Switzerland.
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland.
Dalton Trans. 2017 Mar 14;46(11):3443-3448. doi: 10.1039/c7dt00070g.
A rhodium complex containing a tetrapodal triolefin ligand (tropP) and a phosphanyl ligand (PPh) has been prepared and characterised. The special structural confinements of the tetradentate ligand impose an unusually long Rh-PPh bond. Chemical oxidation of the complex with FcOTf affords [Rh(OTf)(tropP)] and plausibly phosphanyl radicals, which react instantly with a spin trap reagent forming a nitroxide-based persistent radical, undergo HAT with silanes or dimerise to the corresponding diphosphine (PPh). Chemical oxidation with a peroxide leads to complex [Rh(POPh)(tropP)] which is photolabile and loses the PhPO moiety upon irradiation with UV/Vis light in CHCl.
一种含有四足三烯烃配体（tropP）和膦基配体（PPh）的铑配合物已被制备并表征。四齿配体的特殊结构限制导致Rh-PPh键异常长。用FcOTf对该配合物进行化学氧化得到[Rh(OTf)(tropP)]以及可能的膦基自由基，这些自由基会立即与自旋捕获试剂反应形成基于氮氧化物的持久自由基，与硅烷发生氢原子转移反应或二聚形成相应的二膦（PPh）。用过氧化物进行化学氧化会生成配合物[Rh(POPh)(tropP)]，该配合物对光不稳定，在CHCl中用紫外/可见光照射时会失去PhPO部分。
