A Neutral Organometallic Fluoro Complex Can Be a Good Ligand

The reaction of the complex [Mo(OTf)(η 3 ‐C 3 H 4 ‐Me‐2)(CO) 2 (phen)] ( 1 ) (OTf = trifluoromethylsulfonate; phen = 1,10‐phenanthroline) with tetrabutylammonium fluoride trihydrate afforded the fluoride complex [MoF(η 3 ‐C 3 H 4 ‐Me‐2)(CO) 2 (phen)] ( 2 ). The IR spectrum and the oxidation potential of 2 reflect the fact that its metal center is more electron‐rich than that of the chloro analogue [MoCl(η 3 ‐C 3 H 4 ‐Me‐2)(CO) 2 (phen)]. Compound 2 reacted with 1 affording the homobinuclear complex [{Mo(η 3 ‐C 3 H 4 ‐Me‐2)(CO) 2 (phen)} 2 (μ‐F)][OTf] ( 3 ), with a fluoride bridge. Compound 2 also reacts with the species generated in situ by triflate abstraction from [M(OTf)(CO) 3 (′NN′)] (M = Mn, Re; ′NN′ = 2,2′‐bipyridine (bipy), phen) using NaBAr′ 4 (Ar′ = 3,5‐bis(trifluoromethyl)phenyl), affording the heterobinuclear complexes [{Mo(η 3 ‐C 3 H 4 ‐Me‐2)(CO) 2 (phen)}(μ‐F){M(CO) 3 (′NN′)}][BAr′ 4 ] (M = Mn, ′NN′ = bipy ( 4 ); M = Re, ′NN′ = phen ( 5 )). All new compounds have been characterized by spectroscopic methods (IR and NMR) and, in the case of 1 , 2 , 3 , and 4 , also by means of X‐ray diffraction analysis.