Complexes [Fe(CO)4(RPCl2)] (2) (a: R = CPh3, b: R = tBu) were used to generate the first examples of phosphinidenoid iron(0) complexes [Li(12-crown-4)(solv)n][Fe(CO)4(RPCl] (3a,b), characterized by NMR spectroscopy.
Synthesis of the first P-CPh 3 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 ad 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 ringexpansion 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.
After more than 160 years of oxirane (epoxide) chemistry, the first derivative of a phosphorus analogue, namely oxaphosphirane, has been synthesized. Reactions with borane sulfane, peroxy compounds and elemental sulfur,...
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