An Unusual Product from the Reaction of C(PPh 3 ) 2 with [Mn 2 (CO) 10 ]: Formation and Crystal Structure of [Mn(OPPh 3 ) 2 {O 2 CC(PPh 3 ) 2 } 2 ][Mn(CO) 5 ] 2

The carbodiphosphorane C(PPh 3 ) 2 ( 1 ) reacts with [Mn 2 (CO) 10 ] in THF to produce quantitatively the salt‐like complex (HC{PPh 3 } 2 )[Mn(CO) 5 ] ( 2 ) as THF solvate. If the reaction is carried out in 1,2‐dimethoxyethane (DME) small amounts of [Mn(OPPh 3 ) 2 {O 2 CC(PPh 3 ) 2 } 2 ][Mn(CO) 5 ] 2 ( 3 ) as DME solvate along with solvent free 2 as the main product were isolated. Proton abstraction from the solvent led to the formation of 2 ; the ligands OPPh 3 and O 2 CC(PPh 3 ) 2 } 2 of 3 are the results of a side reaction from [Mn 2 (CO) 10 ] and 1 in a Wittig type manner. From the reaction in benzene small amounts of 3 were also obtained, crystallizing as benzene solvate 3· 4C 6 H 6 . The crystal structures of 2· THF, 2 , 3· 1.75DME and 3· 4C 6 H 6 are reported. The compounds are further characterized by IR and 31 P NMR spectroscopy.