Dinuclear molybdenum complexes derived from diphenols: electrochemical interactions and reduced species

Abdul-Rahman, Azilah ; Amoroso, Angelo A. ; Branston, Timothy N. ; Das, Amitava ; Maher, John P. ; McCleverty, Jon A. ; Ward, Michael D. (1997) Dinuclear molybdenum complexes derived from diphenols: electrochemical interactions and reduced species Polyhedron, 16 (24). pp. 4353-4362. ISSN 0277-5387

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Official URL: http://www.sciencedirect.com/science/article/pii/S...

Related URL: http://dx.doi.org/10.1016/S0277-5387(97)00199-X

Abstract

The new diphenolato complexes [{Mo(NO){HB(dmpz)3}Cl}2Q] where dmpz = 3,5-dimethylpyrazolyl and Q = OC6H4(C6H4O (n = 1 or 2), OC6H4CR=CRC6H4O (R = H or Et), and OC6H4CH=CHC6H4CH=CHC6H4O have been prepared and their electrochemical properties (cyclic and differential pulse voltammetry) compared with previously reported analogues where Q = OC6H4O, OC6H4EC6H4O (E = SO2, CO and S), OC6H4 (CO)C6H4 C6H4(CO)C6H4O and 1,5- and 2,7-O2C10H6. The electrochemical interaction between the redox centres in the new complexes is very weak, in contrast to that in the 1,4-benzenediolato and naphthalendiolato species. The EPR spectra of the reduced mixed-valence species [{Mo(NO){HB(dmpz)3}Cl}2Q]- where Q = 1,3- and 1,4-OC6H4O and OC6H4SC6H4O shows that they are valence-trapped at room temperature, whereas those of the dianions [{Mo(NO){HB(dmpz)3}Cl}2Q]2- where Q = 1,4-OC6H4O, OC6H4EC6H4O (E = CO or S) and OC6H4CH=CHC6H4CH=CHC6H4O shows that the unpaired spins on each molybdenum centre are strongly correlated (J, the spin exchange integral AMo, the metal-hyperfine coupling constant). The electrochemical properties and the comproportionation constants for the reaction [{Mo(NO){HB(dmpz)3} Cl}2Q] + [{Mo(NO){HB(dmpz)3}Cl}O]2]2-↩2[{Mo(NO) {HB(dmpz)3}Cl}2Q]- where Q = diphenolato bridge, are compared with related compounds containing benzenediamido and dianilido bridges.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
Keywords:Nitrosyl; Tris(pyrazolyl)borate; Molybdenum; Spin Correlation; Electrochemical Interaction; Diphenols
ID Code:59915
Deposited On:07 Sep 2011 14:17
Last Modified:07 Sep 2011 14:17

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