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

Journal Article · Wed Jan 16 04:00:00 EST 1991 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00002a018· OSTI ID:5289735

Lehmann, R E; Kochi, J K ^[1]

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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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CRYSTALLOGRAPHY
DATA
DIENES
DIFFRACTION
EXPERIMENTAL DATA
FERROCENE
HYDROCARBONS
INFORMATION
IRON COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYENES
SCATTERING
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION