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

doi:10.1021/ic800693r

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 journal › Article › peer-review

11 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 language	English
Pages (from-to)	9248-9255
Number of pages	8
Journal	Inorganic Chemistry
Volume	47
Issue number	20
Early online date	26 Sept 2008
DOIs	https://doi.org/10.1021/ic800693r
Publication status	Published - 20 Oct 2008
Externally published	Yes

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@article{bd012981bf494d8f8702e226a58e4ba7,

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",

year = "2008",

month = oct,

day = "20",

doi = "10.1021/ic800693r",

language = "English",

volume = "47",

pages = "9248--9255",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

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.

UR - https://www.scopus.com/pages/publications/55249120038

U2 - 10.1021/ic800693r

DO - 10.1021/ic800693r

M3 - Article

AN - SCOPUS:55249120038

SN - 0020-1669

VL - 47

SP - 9248

EP - 9255

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

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

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