Starting from [Mn(C 5 H 4 Br)(PPh 3 )(CO) 2 ] (1a), the cymantrenyl thioethers [Mn(C 5 H 4 SMe)(PPh 3 )(CO) 2 ] (1b) and [Mn{C 5 H 4-n Br(SMe) n }(PPh 3 )(CO) 2 ] (n = 1 for compound 2, n = 2 for 3 and n = 3 for 4) were obtained, using either n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or lithium tetramethylpiperidide (LiTMP) as base, followed by electrophilic quenching with MeSSMe. Stepwise consecutive reaction of [Mn(C 5 Br 5 )(PPh 3 )(CO) 2 ] with n-BuLi and MeSSMe led finally to [Mn{C 5 (SMe) 5 }(PPh 3 )(CO) 2 ] (11), only the fifth complex to be reported containing a perthiolated cyclopentadienyl ring. The molecular and crystal structures of 1b, 3, 4 and 11 were determined and were studied for the occurrence of S...S and S...Br interactions. It turned out that although some interactions of this type occurred, they were of minor importance for the arrangement of the molecules in the crystal.