Crystal and molecular structures of fac‐[Re(Bid)(PPh3)(CO)3] [Bid is tropolone (TropH) and tribromotropolone (TropBr3H)].

Two rhenium complexes, namely, fac‐tricarbonyl(triphenylphosphane‐κP)(tropolonato‐κ2O,O′)rhenium(I), [Re(C7H5O2)(C18H15P)(CO)3] or fac‐[Re(Trop)(PPh3)(CO)3] (1), and fac‐tricarbonyl(3,5,7‐tribromotropolonato‐κ2O,O′)(triphenylphosphane‐κP)rhenium(I), [Re(C7H2Br3O2)(C18H15P)(CO)3] or fac‐[Re(TropBr3)(PPh3)(CO)3] (2) (TropH is tropolone and and TropBr3H is tribromotropolone), were synthesized and their crystal and molecular structures confirmed by single‐crystal X‐ray diffraction. Both crystallized in the space group P and display an array of inter‐ and intramolecular interactions which were confirmed by solid‐state 13C NMR spectroscopy using cross polarization magic angle spinning (CPMAS) techniques, as well as Hirshfeld surface analysis. The slightly longer Re—P distance of 1 [2.4987 (5) versus 2.4799 (11) Å for 1 and 2, respectively] suggests stronger back donation from the carbonyl groups in the former case, possibly due to the stronger electron‐donating ability of the unsubstituted tropolonate ring system. However, this is not supported in the Re—CO bond distances of 1 and 2. [ABSTRACT FROM AUTHOR]