Dimolybdenum Bis-2,4,6-triisopropyl-benzoate Bis-4-isonicotinate: A Redox Active Analogue of 4,4′-Bipyridine with Ambivalent Properties

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

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Date of publication of this fulltext: 07 Jun 2010 12:22

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Details

Item type:	Article
Date:	26 September 2008
Institutions:	Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer
Identification Number:	Value Type 10.1021/ic800693r DOI
Dewey Decimal Classification:	500 Science > 540 Chemistry & allied sciences
Status:	Published
Refereed:	Unknown
Created at the University of Regensburg:	Unknown
Item ID:	15105

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Abstract

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 ...

Abstract

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 quasi-metalloorganic 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-Mo2(TiPB)2(nic)2](PF6)2, III, and [(1,5-COD)Pt(μ-I)(PF6)2]n.

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Metadata last modified: 03 Jun 2018 16:12

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