Synthesis, structure and DFT study of dinuclear iron, cobalt and nickel complexes with cyclopentadienyl-metal moieties†
Abstract
Reactions of 1,1′-bis(dipheny1phosphino)cobaltocene with Co(PMe3)4, Ni(PMe3)4, Fe(PMe3)4, Ni(COD)2, FeMe2(PMe3)4 or NiMe2(PMe3)3 afford a series of novel dinuclear complexes [((Me3P)![[lower bond 1 start]](https://www.rsc.org/images/entities/char_e012.gif) Co(η5-C5H4
Co(η5-C5H4![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif) PPh2))((Me3P)M
PPh2))((Me3P)M![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif) (η5-C5H4P
(η5-C5H4P![[lower bond 1 end]](https://www.rsc.org/images/entities/char_e013.gif) Ph2))] (M = Co(1), Ni(2) and Fe(3)) [Co(η5-C5H4
Ph2))] (M = Co(1), Ni(2) and Fe(3)) [Co(η5-C5H4![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif) PPh2)2Ni
PPh2)2Ni![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif) (COD)](4), [Co(η5-C5H4
(COD)](4), [Co(η5-C5H4![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif) PPh2)2Ni
PPh2)2Ni![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif) (PMe3)2] (5) and [((Me3P)
(PMe3)2] (5) and [((Me3P)![[lower bond 1 start]](https://www.rsc.org/images/entities/char_e012.gif) Co(Me)(η5-C5H4
Co(Me)(η5-C5H4![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif) PPh2))((Me3P)Fe
PPh2))((Me3P)Fe![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif) (Me)(η5-C5H4P
(Me)(η5-C5H4P![[lower bond 1 end]](https://www.rsc.org/images/entities/char_e013.gif) Ph2))] (6). Reactions of 1,1′-bis(dipheny1phosphino)ferrocene with Ni(PMe3)4, NiMe2(PMe3)3, or Co(PMe3)4 gives rise to complexes [Fe(η5-C5H4
Ph2))] (6). Reactions of 1,1′-bis(dipheny1phosphino)ferrocene with Ni(PMe3)4, NiMe2(PMe3)3, or Co(PMe3)4 gives rise to complexes [Fe(η5-C5H4![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif) PPh2)2M
PPh2)2M![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif) (PMe3)2] (M = Ni (7), Co (8)). The complexes 1–8 were spectroscopically investigated and studied by X-ray single crystal diffraction. The possible reaction mechanisms and structural characteristics are discussed. Density functional theory (DFT) calculations strongly support the deductions.
(PMe3)2] (M = Ni (7), Co (8)). The complexes 1–8 were spectroscopically investigated and studied by X-ray single crystal diffraction. The possible reaction mechanisms and structural characteristics are discussed. Density functional theory (DFT) calculations strongly support the deductions.
 
                



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