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

Research output: Contribution to journalArticle

10 Citations (Scopus)

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 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
Volume47
Issue number20
Early online date26 Sep 2008
DOIs
Publication statusPublished - 20 Oct 2008
Externally publishedYes

Fingerprint

Benzoates
analogs
solid state
formic acid
crack opening displacement
Molecular structure
molecular structure
nicotinic acid
Ligands
ligands
Niacin
formates
Dimethyl Sulfoxide
Discrete Fourier transforms
assemblies
Electronic structure
ethyl alcohol
Ethanol
Single crystals
Oxygen

Cite this

Chisholm, Malcolm H. ; Dann, Angela S. ; Dielmann, Fabian ; Gallucci, Judith C. ; Patmore, Nathan J. ; Ramnauth, Ramkrishna ; Scheer, Manfred. / Dimolybdenum bis-2,4,6-triisopropyl-benzoate bis-4-isonicotinate : A redox active analogue of 4,4′-bipyridine with ambivalent properties. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 20. pp. 9248-9255.
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title = "Dimolybdenum bis-2,4,6-triisopropyl-benzoate bis-4-isonicotinate: A redox active analogue of 4,4′-bipyridine with ambivalent properties",
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 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.",
author = "Chisholm, {Malcolm H.} and Dann, {Angela S.} and Fabian Dielmann and Gallucci, {Judith C.} and Patmore, {Nathan J.} and Ramkrishna Ramnauth and Manfred Scheer",
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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.; Patmore, Nathan J.; Ramnauth, Ramkrishna; Scheer, Manfred.

In: Inorganic Chemistry, Vol. 47, No. 20, 20.10.2008, p. 9248-9255.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Dimolybdenum bis-2,4,6-triisopropyl-benzoate bis-4-isonicotinate

T2 - A redox active analogue of 4,4′-bipyridine with ambivalent properties

AU - Chisholm, Malcolm H.

AU - Dann, Angela S.

AU - Dielmann, Fabian

AU - Gallucci, Judith C.

AU - Patmore, Nathan J.

AU - Ramnauth, Ramkrishna

AU - Scheer, Manfred

PY - 2008/10/20

Y1 - 2008/10/20

N2 - 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.

AB - 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.

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U2 - 10.1021/ic800693r

DO - 10.1021/ic800693r

M3 - Article

VL - 47

SP - 9248

EP - 9255

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -