Abstract
The coordination chemistry of 2‐(2′‐pyridyl)‐4,6‐diarylphosphinines towards ReI has been investigated and compared to the structurally analogous 2,2′‐bipyridine derivatives. The different steric properties of the chelating pyridylphosphinines with respect to substituted bipyridines lead to considerable differences in the structures of the mononuclear [(P^N)Re(CO)3X] and [(N^N)Re(CO)3X] (X = Cl, Br) complexes, both in the solid state and in solution. The phosphinine‐based coordination compounds are highly sensitive towards nucleophilic attack and react reversibly with water at the P=C double bond.
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