Abstract
AbstractSynthesis of the first P‐CPh3 substituted oxaphosphirane iron(0) complexes was achieved, representing a more cost‐efficient access to these versatile ligands. While reactions with very electron‐deficient aldehydes such as pentafluoro‐ and 3,5‐bis(trifluoromethyl)‐benzaldehyde were selective to give oxaphosphirane complexes 3 a,b, those with less electronically activated benzaldehydes were very sensitive towards traces of water, and oxaphosphirane complexes 6 a–d were obtained as mixtures with the hydroxyphosphane iron complex 5 in competing reactions. As a case in point, complex 3 a was converted into 1,3,4‐oxazaphospholane complex 6 using an acid‐induced ring‐expansion protocol and acetonitrile. The formation of oxaphosphirane complexes from Li/Cl phosphinidenoid complexes and carbonyl units was studied for the first time through theoretical calculations using appropriate model species.
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