Electrochemistry of a series of hexakis(aryl isocyanide)chromium(0) complexes

Essenmacher, G. J.; Treichel, P. M.

doi:10.1021/ic50170a015

Cited by 42 publications

(11 citation statements)

References 35 publications

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“…The hexakis (2,6-diisopropylphenyl isocyanide)chromium(0) was synthesized from Cr2(CH3CO)4(H20) by a standard method (Essenmacher & Treichel, 1977). The chromium acetate, isocyanide and dry ethanol were kept under nitrogen during the entire process.…”

Section: Methodsmentioning

confidence: 99%

Structure of hexakis(2,6-diisopropylphenyl isocyanide)chromium(0)

Anderson¹,

Scott²,

Wherland³

et al. 1991

Acta Crystallogr C

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Section: Methodsmentioning

confidence: 99%

Structure of hexakis(2,6-diisopropylphenyl isocyanide)chromium(0)

Anderson¹,

Scott²,

Wherland³

et al. 1991

Acta Crystallogr C

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“…Recently, we reported an approach to overcoming this challenge by using the rigid and linear ditopic m -terphenyl diisocyanide, [CNAr Mes2 ] 2 , as a linker group (Ar Mes2 = 2,6-(2,4,6-Me 3 C 6 H 2 ) 2 C 6 H 3 ; Scheme ). , Isocyanide ligands have long been recognized for their ability to function as both good σ-donors and strong π-acids, − which are properties that are particularly advantageous for the stabilization of electron-rich metal centers. − Accordingly, despite their charge neutrality, the dual bonding interactions provided by isocyanides lead to strong metal–ligand linkages that can be harnessed for reticular network formation. ,, It was shown that [CNAr Mes2 ] 2 could provide a series of robust, single-crystalline frameworks featuring Cu(I)-based single-metal structural nodes (i.e., Cu- ISO CNs 1–3; ISO CN = isocyanide coordination network; Scheme ). In certain cases, these frameworks retain their thermal integrity up to ca.…”

Section: Introductionmentioning

confidence: 99%

Aqueous Stability and Ligand Substitution of a Layered Cu(I)/Isocyanide-Based Organometallic Network Material with a Well-Defined Channel Structure

et al. 2020

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Isocyanide coordination networks (ISOCNs), which consist of multitopic isocyanide linker groups and transition-metal-based secondary building units (SBUs), are a promising class of organometallic framework materials for the inclusion of low-valent metal centers as primary structural components. Previously, it was demonstrated that the ditopic m-terphenyl isocyanide ligand, [CNArMes2]2 (ArMes2 = 2,6-(2,4,6-Me3C6H2)2C6H3), could provide single-metal node frameworks based on Cu(I) and Ni(0) centers. However, the relatively short linker length in [CNArMes2]2 precluded the formation of networks with significant porosity. Here, it is shown that expansion of the [CNArMes2]2 scaffold with a central phenylene spacer allows for the formation of a robust Cu(I)-based framework with a distinct and solvent accessible channel structure. This new framework, denoted Cu-ISOCN-4, is prepared as single-crystalline samples from a solvothermal reaction between [Cu(NCMe)4]PF6 and expanded linker 1,4-(CNArMes2)2C6H4. Crystallographic characterization of Cu-ISOCN-4 revealed mononuclear [Cu(THF)(CNR)3]+ structural nodes. The expanded diisocyanide linker results in fourfold interpenetrated (6,3) internal morphology. However, interpenetration in Cu-ISOCN-4 results in discrete layer domains, each of which possesses well-defined 29 × 19 Å channels along the crystallographic b axis. Thermogravimetric analysis on Cu-ISOCN-4 revealed THF solvent loss from the channels between 100–200 °C and dissociation of the Cu-coordinated THF ligand at 290 °C. The overall integrity of the network remains intact up to 400 °C, thereby signifying the robust nature of materials produced from metal-isocyanide M-C linkages. Aqueous stability studies revealed that Cu-ISOCN-4 remains chemically resistant to exposure to liquid water for several days. In addition, ligand exchange studies in both THF and aqueous solution demonstrate that the Cu-coordinated THF group in Cu-ISOCN-4 can be readily substituted with pyridine. This ligand exchange process occurs via single-crystal-to-single-crystal transformations and can also be readily monitored by infrared spectroscopy.

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“…Analysis of the mass spectrum of the reaction mixture indicated that partial oxidation of the tungsten complex occurred. Essenmacher and Treichel reported similar oxidations of Cr(0) complexes when they were allowed to react with aryl isocyanides which contained strongly electron-withdrawing substituents …”

Section: Methodsmentioning

confidence: 92%

Conformational Isomerism in (p-RC₆H₄NC)₂W(dppe)₂: Substantial Structural Changes Resulting from Subtle Differences in the π-Acidity ofp-RC₆H₄NC

2000

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Bis(arylisocyanide) complexes of tungsten containing bulky bidentate aryl phosphine ligands adopt either cis or trans conformations, depending on the nature of the para-substituent group on the aryl isocyanide ligand. Ab initio calculations on a series of ligands, p-RC 6 H 4 NC, indicate that the energy of the LUMO is determined by the electron-withdrawing/donating capabilities of the substituent group, which determine the relative π-acidity of the ligand. Strong π acids, which contain electron-withdrawing groups, tend to polarize sufficient charge density away from the metal center to effect the formation of the sterically less favorable, but electronically stabilized, cis conformer. Weaker π acids, containing donor substituents, do not provide enough electronic stabilization to overcome steric repulsion, resulting in the adoption of trans geometry. (CNC 6 H 4 NC)W(dppe) 2 exists as the cis conformer, as does (CNC 6 H 2 (CH 3 ) 2 NC)W(dppe) 2 , while (CNC 6 (CH 3 ) 4 -NC)W(dppe) 2 , with increased steric bulk coupled with decreased π-acidity, exists as the trans conformer. Theoretical and experimental studies indicate that the energy match between isocyanide ligands and the metal center can be modified significantly by the selection of various substituents and that relatively subtle variations in the electronic structure of the ligands can have dramatic effects on the structures of the resulting complexes.

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Electrochemistry of a series of hexakis(aryl isocyanide)chromium(0) complexes

Cited by 42 publications

References 35 publications

Structure of hexakis(2,6-diisopropylphenyl isocyanide)chromium(0)

Structure of hexakis(2,6-diisopropylphenyl isocyanide)chromium(0)

Aqueous Stability and Ligand Substitution of a Layered Cu(I)/Isocyanide-Based Organometallic Network Material with a Well-Defined Channel Structure

Conformational Isomerism in (p-RC₆H₄NC)₂W(dppe)₂: Substantial Structural Changes Resulting from Subtle Differences in the π-Acidity ofp-RC₆H₄NC

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Electrochemistry of a series of hexakis(aryl isocyanide)chromium(0) complexes

Cited by 42 publications

References 35 publications

Structure of hexakis(2,6-diisopropylphenyl isocyanide)chromium(0)

Structure of hexakis(2,6-diisopropylphenyl isocyanide)chromium(0)

Aqueous Stability and Ligand Substitution of a Layered Cu(I)/Isocyanide-Based Organometallic Network Material with a Well-Defined Channel Structure

Conformational Isomerism in (p-RC6H4NC)2W(dppe)2: Substantial Structural Changes Resulting from Subtle Differences in the π-Acidity ofp-RC6H4NC

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Conformational Isomerism in (p-RC₆H₄NC)₂W(dppe)₂: Substantial Structural Changes Resulting from Subtle Differences in the π-Acidity ofp-RC₆H₄NC