Orthomanganation of the iminophosphorane Ph 3PNPh, and of triphenylarsine-oxide and -sulfide

Abstract

Two novel types of cyclometallated rings are described. Orthomanganation of Ph 3PNPh gave Ph 2P[ NPh]C 6H 4M n(CO) 4, 5a, containing an N,C-chelated five-membered ring, characterised by single crystal X-ray determinations of two distinct polymorphs. Solutions of 5a are thermochroic. The rhenium analogue of 5a was also prepared. Reaction of Ph 3AsX (XO, S) with PhCH 2Mn(CO) 5 gave the first examples of orthometallated triphenylarsine chalcogenides. The example with XO was characterised structurally. Attempted cyclomanganation of Ph 3As was unsuccessful, but gave (in low yield) a dimanganese complex containing μ-AsPh 2 and μ–η 1,η 6-benzyl ligands.