The synthesis and characterization of two series of rhenium carbonyl complexes with P- coordinated phosphinoalkynes are reported. The anionic fac-[ReBr2 (CO) 3 (Ph2PCCR)]− and neutral fac-[ReBr (CO) 3 (Ph2PCCR) 2](R= Ph, Tol, tBu) complexes have been prepared and the crystal structures of fac-[ReBr2 (CO) 3 (Ph2PCCTol)]− and fac-[ReBr (CO) 3 (Ph2PCCtBu) 2] have been determined by X-ray crystallography, evidencing the ...