Aryl M(κ 1 -Ar)(CO) n P 5−n [M=Mn, Re; Ar=C 6 H 5 , 4-CH 3 C 6 H 4 ; n=2, 3; P=P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt] and Re(κ 1 -C 6 H 5 )(CO) 3 [Ph 2 PO(CH 2 ) 3 OPPh 2 ] complexes were prepared by allowing hydrides MH(CO) n P 5−n to react first with triflic acid and then with the appropriate aryl lithium (LiAr) compounds. The complexes were characterized spectroscopically (IR and 1 H, 31 P, 13 C NMR) and by the X-ray crystal structure determination of Re(κ 1 -C 6 H 5 )(CO) 3 [Ph 2 PO(CH 2 ) 3 OPPh 2 ] derivative. Protonation reaction of the aryl complexes with HBF 4 ·Et 2 O lead to free hydrocarbons Ar–H and the unsaturated [M(CO) n P 5−n ] + cations, separated as solids in the case of [Re(CO) 3 P 2 ]BF 4 derivatives.