Browsing Research articles (Dept of Chemistry) by Author "Becker, C.A.L."
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Ahmad, J.; Bothata-Nareetsile, F.; Becker, C.A.L. (NRC Research Press, http://www.nrcresearchpress.com/loi/cjc, NaN, 2003)[more][less]
Abstract: Nine pairs of corresponding [CoI(CNR)3(PR3 ′ )2]X, [CoII(CNR)3(PR3 ′ )2]X2 complexes — where X = ClO4, BF4; CNR = CNCMe3, CNCHMe2, CNC6H11, CNCH2Ph; PR3′ = PPh3, P(C6H4Me-p)3, P(C6H4OMe-p)3 — have been studied using cyclic voltammetry in CH3CN solutions. All cycles are reversible, and E1/2 for the Co(I) complexes, initially oxidized, are within experimental error identical to E1/2 values for the corresponding Co(II) complexes, initially reduced. E1/2 values are strongly dependent on the triarylphosphine ligand, decreasing in the order PPh3 > > P(C6H4Me-p)3 > P(C6H4OMe-p)3, and weakly dependent on the alkylisocyanide ligand, decreasing in the order CNCH2Ph > CNCMe3 > CNC6H11 ≥ CNCHMe2. Solution ν(-N C) IR patterns reveal that the [CoI(CNR)3(PR3′)2]X complexes do not have regular trigonal bipyramidal coordination, their structure being determined by the particular CNR ligand, while the [CoII(CNR)3(PR3′)2]X2 complexes, specifically in CF3CH2OH, appear to have regular trigonal bipyramidal coordination. Description: Signs on the abstract may be different to the original document URI: http://hdl.handle.net/10311/1034 Files in this item: 1
Ahmad_CJC_2003.pdf (782.1Kb) -
Oyetunji, O.A.; Paphane, B.D.; Becker, C.A.L. (Springer, http://www.springer.com/chemistry/journal/11243, NaN, 2006)[more][less]
Abstract: The interaction of pyridine with four tetraki(arylisocyanide)cobalt(II) complexes, [Co(CNR)4(ClO4)2] R = 2,6- Me2C6H3 (A), 2,4,6-Me3C6H2 (B), 2,6-Et2C6H3 (C) and 2,6-iPr2C6H3 (D), have been studied in 2,2,2-trifluoroethanol medium. The kinetics of the reactions were investigated over the 293–318 K temperature range. The reaction profile exhibited two distinct processes, proposed to be an initial fast substitution followed by a slow reduction, for each of the reactions. The pseudo first-order rate constants for both processes increased with increasing concentration of pyridine with the reduction processes exhibiting saturation kinetics at high pyridine concentrations. Steric hindrance plays a significant role in the rates of the reactions, as the rates decrease in the order k(A) > k(B) > k(C) > k(D). The activation enthalpies, DH , increase from A to D while the activation entropies, DS , are relatively similar for the four reactions, indicating similar transition states and hence similar mechanisms. Complex B was first synthesized and characterized in this study. URI: http://hdl.handle.net/10311/1033 Files in this item: 1
Oyetunji_TMC_2006.pdf (911.4Kb)
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