TY - JOUR
T1 - Intermetal coupling in [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) and in their dicationic and monocationic mixed-valence forms
AU - Chung, Min Chul
AU - Gu, Xinhong
AU - Etzenhouser, Beth A.
AU - Spuches, Anne Marie
AU - Rye, Peter T.
AU - Seetharaman, Sripriya K.
AU - Rose, David J.
AU - Zubieta, Jon
AU - Sponsler, Michael B.
PY - 2003/8/18
Y1 - 2003/8/18
N2 - The butadienediyl-bridged complexes [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) (R = H, Me) and their radical cationic and dicationic forms have been prepared and characterized by cyclic voltammetry, electronic spectroscopy (UV-vis and near-IR), EPR, and X-ray crystallography (R = Me). Comparisons with each other and with the literature complexes [(η5-C5R 5)Fe(dppm)]2(μ-CH=CHCH=CH), [(η5-C 5Me5)Fe(dppe)]2(μ-C≡CC≡C), and [(η5-C5Me5)-Fe(dppe)] 2(μ-C(OMe)=CHCH=C(OMe)) have allowed for systematic evaluation of several structural variations (C5H5 vs C 5Me5, dppm vs dppe, μ-CH=CHCH=CH vs μ-C≡CC≡C, and μ-CH=CHCH=CH vs μ-C(OMe)=CHCH=C(OMe)) and their effects on spectra and electronic intermetal coupling. Some of the structural changes have opposite effects on Hab, the effective coupling parameter, and Kc, the comproportionation constant. The data for the mixed-valence cations are most consistent with electronic delocalization.
AB - The butadienediyl-bridged complexes [(η5-C5R 5)Fe(dppe)]2(μ-CH=CHCH=CH) (R = H, Me) and their radical cationic and dicationic forms have been prepared and characterized by cyclic voltammetry, electronic spectroscopy (UV-vis and near-IR), EPR, and X-ray crystallography (R = Me). Comparisons with each other and with the literature complexes [(η5-C5R 5)Fe(dppm)]2(μ-CH=CHCH=CH), [(η5-C 5Me5)Fe(dppe)]2(μ-C≡CC≡C), and [(η5-C5Me5)-Fe(dppe)] 2(μ-C(OMe)=CHCH=C(OMe)) have allowed for systematic evaluation of several structural variations (C5H5 vs C 5Me5, dppm vs dppe, μ-CH=CHCH=CH vs μ-C≡CC≡C, and μ-CH=CHCH=CH vs μ-C(OMe)=CHCH=C(OMe)) and their effects on spectra and electronic intermetal coupling. Some of the structural changes have opposite effects on Hab, the effective coupling parameter, and Kc, the comproportionation constant. The data for the mixed-valence cations are most consistent with electronic delocalization.
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U2 - 10.1021/om0300979
DO - 10.1021/om0300979
M3 - Article
AN - SCOPUS:0041825169
SN - 0276-7333
VL - 22
SP - 3485
EP - 3494
JO - Organometallics
JF - Organometallics
IS - 17
ER -