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Structures and photoactivation of charge-transfer complexes of bis(arene)iron(II) dications with ferrocene and arene donors

Journal Article · · Journal of the American Chemical Society; (United States)
DOI:https://doi.org/10.1021/ja00002a018· OSTI ID:5289735
;  [1]
  1. Univ. of Houston, University Park, TX (USA)

Ferrocene forms a series of unusual charge-transfer crystals with the isoelectronic bis(arene)iron(II) dication, in which X-ray crystallography establishes the alternate (heterosoric) stacking of sandwich structures comprising the donor-acceptor pairs. In acetonitrile, the 1:1 complex (Cp{sub 2}Fe, Ar{sub 2}Fe{sup 2+}) shows a broad absorption band centered at {lambda}{sub max} {approximately} 630 nm. Bis(arene)iron(II) acceptors also form highly colored crystals with various arene donors, in which the charge-transfer absorption (hv{sub CT}) derives from the same heterosoric stacking of donor-acceptor pairs-despite the structurally divergent nature of the arene (planar) and ferrocene (sandwich) donors. These absorptions undergo a predictable red-shift with increasing acceptor strength in the order (BZ){sub 2}Fe{sup 2+} > (MES){sub 2}Fe{sup 2+} > (DUR){sub 2}Fe{sup 2+} > (HMB){sub 2}Fe{sup 2+}, as judged by the reduction potentials E {sub red} of the benzene, mesitylene, durene, and hexamethylbenzene derivatives, respectively.

OSTI ID:
5289735
Journal Information:
Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 113:2; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English