Synthesis, spectroscopic characterization and reactivities of linear and butterfly chromium/selenium complexes containing substituted cyclopentadienyl ligands: crystal structures of [{η5-MeC5H4Cr(CO)2}2Se] and [{η5-EtO2CC5H4Cr(CO)2}2Se2]

The Cr–Cr singly-bonded dimers [{η5-RC5H4Cr(CO)3}2] (1, R=Me; 2, R=CO2Et) reacted with an equivalent of elemental selenium in THF at room temperature to give the linear Cr2Se complexes [{η5-RC5H4Cr(CO)2}2Se] (3, R=Me; 4, R=CO2Et), whereas the linear Cr2Se complex (5, R=MeCO) reacted with excess NaBH4, Ph3PCHPh or 2,4-dinitrophenylhydrazine under respective conditions to afford the linear Cr2Se derivatives [{η5-RC5H4Cr(CO)2}2Se] (6, R=MeCH(OH); 7, R=PhCHCMe; 8, R=2,4-(NO2)2C6H3NHNCMe). Similarly, while the butterfly Cr2Se2 complexes [{η5-RC5H4Cr(CO)2}2Se2] (9, R=Me; 10, R=CO2Et) could be produced either by reaction of dimers 1 and 2 with an excess amount of elemental selenium, or by reaction of the linear complexes 3 and 4 with an equivalent of elemental selenium, the butterfly Cr2Se2 derivatives [{η5-RC5H4Cr(CO)2}2Se2] (12, R=MeCH(OH); 13, R=PhCHCMe; 14, R=2,4-(NO2)2C6H3NHNCMe) were yielded by reaction of the butterfly Cr2Se2 complex (11, R=MeCO) with an excess quantity of NaBH4, Ph3PCHPh and 2,4-dinitrophenylhyazine. Both the linear complexes 3, 4, 6–8 and the butterfly complexes 9, 10, 12–14 are new, which have been fully characterized by elemental analysis, spectroscopy and X-ray crystallography.