Synthesis and characterization of unsaturated Manganese(I) and Rhenium(I) dicarbonyl complexes supported by an anionic PNP pincer

Abstract Syntheses of Re and Mn carbonyl complexes of the diarylamido/bis(phosphine) PNP pincer ligand are reported. The saturated (PNP)Re(CO) 3 and (PNP)Mn(CO) 3 react cleanly with HBr in acetic acid to undergo decarbonylation with concomitant addition of HBr across the N-M bond. The resultant (PNHP)MBr(CO) 2 (M = Mn or Re) complexes can be dehydrobrominated with trimethylamine to yield the unsaturated (PNP)M(CO) 2 . (PNP)Re(CO) 2 has high affinity for CO and abstracts CO from (PNP)Mn(CO) 3 .