Formation of the Salt‐like Complexes [Co{S 2 CC(PPh 3 ) 2 } 3 ][Co(CO) 4 ] 3 and [(CO) 4 Mn{S 2 CC(PPh 3 ) 2 }][Mn(CO) 5 ] from the Reaction of the Related Carbonyl Compounds with S 2 CC(PPh 3 ) 2

The betain‐like compound S 2 CC(PPh 3 ) 2 ( 1 ), which is obtained from CS 2 and the double ylide C(PPh 3 ) 2 , reacts with [Co 2 (CO) 8 ] and [Mn 2 (CO) 10 ] in THF to afford the salt‐like complexes [Co{S 2 CC(PPh 3 ) 2 } 3 ][Co(CO) 4 ] 3 ( 2 ) and [(CO) 4 Mn{S 2 CC(PPh 3 ) 2 }][Mn(CO) 5 ] ( 3 ), respectively, in good yields. At both d 6 cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co 0 into Co III and Co −I and from Mn 0 into Mn I and Mn −I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by 31 P NMR and IR spectroscopy.