TY - JOUR
T1 - Coupling of CpCr(CO)3 and heterocyclic dithiadiazolyl radicals. Synthetic, X-ray diffraction, dynamic NMR, EPR, CV, and DFT studies
AU - Hiu, Fung Lau
AU - Ang, Pearly Chwee Ying
AU - Ng, Victor Wee Lin
AU - Seah, Ling Kuan
AU - Lai, Yoong Goh
AU - Borisov, Alexey S.
AU - Hazendonk, Paul
AU - Roemmele, Tracey L.
AU - Boeré, René T.
AU - Webster, Richard D.
PY - 2008/1/21
Y1 - 2008/1/21
N2 - The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C6H 4CN2S2)2 (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C6H 3CN2S2)2 (2e) with [CpCr(CO) 3]2 (Cp = η5-C5H5) (1) at ambient temperature respectively yielded the complexes CpCr(CO) 2(η2-S2N2CC6H 4R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF3, 3d) and CpCr(CO)2-(η2-S2N2CC 6H3-S-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)3 (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C6H4-CN2S2Cl (R = OMe, 8c; CF3, 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)2S 2N2CH] and comparisons are made with the reported CpCr(CO)2(π-allyl) complexes.
AB - The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C6H 4CN2S2)2 (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C6H 3CN2S2)2 (2e) with [CpCr(CO) 3]2 (Cp = η5-C5H5) (1) at ambient temperature respectively yielded the complexes CpCr(CO) 2(η2-S2N2CC6H 4R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF3, 3d) and CpCr(CO)2-(η2-S2N2CC 6H3-S-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)3 (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C6H4-CN2S2Cl (R = OMe, 8c; CF3, 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)2S 2N2CH] and comparisons are made with the reported CpCr(CO)2(π-allyl) complexes.
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U2 - 10.1021/ic702128f
DO - 10.1021/ic702128f
M3 - Article
AN - SCOPUS:38949103343
SN - 0020-1669
VL - 47
SP - 632
EP - 644
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -