- Synthesis and structure of singly bridged and doubly bridged [MoFe(3)S(4)] double cubanes with bidentate phosphine ligands.
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The reactions of the (Et(4)N)(2)[(Cl(4)-cat)(MeCN)MoFe(3)S(4)Cl(3)] (I) cluster with Fe(pp)(2)Cl(2) (pp = depe (bis(1,2-diethylphosphino)ethane) or dmpe (bis(1,2-dimethylphosphino)ethane)) produced the [(Cl(4)-cat)MoFe(3)S(4)(pp)(2)Cl](2)(mu-pp) (pp = depe (III) or dmpe (V)) singly bridged double cubanes. The reactions of I with the same bidentate phosphine ligands in the presence of NaBPh(4) also produced III and the [(Cl(4)-cat)MoFe(3)S(4)(dmpe)(2)](2)(mu-S)(mu-dmpe) (VI) doubly bridged double cubane, respectively. The byproduct (BPh(4))[Fe(dmpe)(2)(MeCN)Cl] (VII) has been isolated from the reaction mixture and crystallographically characterized. The depe analogue of VI, [(Cl(4)-cat)MoFe(3)S(4)(depe)(2)](2)(mu-S)(mu-depe) (IV), has been successfully prepared from III in the presence of excess Li(2)S. Similar reactions with (Et(4)N)(2)[Fe(4)S(4)(SPh)(4)] (VIII) have resulted in the formation of the neutral Fe(4)S(4)(depe)(2)(SPh)(2) (IX) cluster. The chloride analogue of IX, Fe(4)S(4)(depe)(2)Cl(2) (XI), has been obtained by a reaction of IX with benzoyl chloride. The crystal and molecular structures of III, VI, VII, and XI have been determined by single-crystal X-ray crystallography. The electrochemical and spectroscopic properties, including the Mossbauer spectra of the new clusters, have been determined and analyzed.
- Han, Jaehong,Coucouvanis, Dimitri
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p. 2738 - 2746
(2008/10/08)
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- Complexes of tertiary phosphines with iron(II) and dinitrogen, dihydrogen, and other small molecules
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The treatment of with sodium borohydride in ethanol produces the hydrides + in high yield.These complexes react with a variety of small molecules including N2 to give further complexes.CO2 and CS2 insert into the iron hydride bond to yield formato- and dithioformato-complexes, respectively, and carboxymethyl acetylene and phenyl acetylene yield a cyclic alkenyl complex and an acetylide, respectively.
- Hills, Adrian,Hughes, David L.,Jimenez-Tenorio, Manuel,Leigh, G. Jeffery
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p. C41 - C44
(2007/10/02)
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