Dimolybdenum bis-2,4,6-triisopropyl-benzoate bis-4-isonicotinate: A redox active analogue of 4,4′-bipyridine with ambivalent properties

Malcolm H. Chisholm, Angela S. Dann, Fabian Dielmann, Judith C. Gallucci, Nathan J. Patmore, Ramkrishna Ramnauth, Manfred Scheer

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The reaction between Mo2(TiPB)4 and 4-iso-nicotinic acid (2 equiv) in ethanol leads to the formation of trans-Mo2(TiPB) 2(nic)2, I, where TiPB = 2,4,6-triisopropylbenzoate and nic = 4-isonicotinate. The molecular structures of I and I·2DMSO were determined in the solid state by a single-crystal X-ray study, and its electronic structure was determined by DFT calculations on a model compound, where formate ligands were substituted for the bulky TiPB. The physicochemical properties of I are reported, and its potential as a redox active building block, a quasimetalloorganic analogue of 4,4′-bipyridine, is described in the synthesis of molecular and solid-state assemblies. The molecular structure of I in the solid state consists of a 3-dimensional network in which each unit of Mo2(TiPB)2(nic)2 acts as a donor and acceptor via N to Mo coordination. In the structure of I·2DMSO, the DMSO ligands coordinate axially with the Mo-Mo bond via oxygen. The reaction between I and Rh2(O2CMe)4 is shown to give a 1-D polymeric chain in the solid state: [{Rh2(O2CMe) 4}{Mo2(TiPB)2(nic)2}] , II. A similar structure was found for the product involving Rh2(O2CCMe3)4. Evidence is also reported for the formation of [(1,5-COD)MePt]2[μ-Mo 2(TiPB)2(nic)2](PF6)2, III, and [(1,5-COD)Pt(μ-I)(PF6)2]n.

Original languageEnglish
Pages (from-to)9248-9255
Number of pages8
JournalInorganic Chemistry
Issue number20
Early online date26 Sep 2008
Publication statusPublished - 20 Oct 2008
Externally publishedYes


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