Renaissance of Isocyanoarenes as Ligands in Low‐Valent Organometallics

Barybin, Mikhail V.; Meyers, John J.; Neal, Brad M.

doi:10.1002/9783527652532.ch14

Cited by 13 publications

(26 citation statements)

References 113 publications

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“…24 applications, including the activation of small molecules (e.g., P 4 and CO 2 ) and as catalysts for hydrogenation and hydroboration reactions. 25 Taking advantage of the wellknown ability of isonitriles to stabilize low-oxidation-state transition-metal complexes, [15][16][17][18]26 in combination with imposing rigidity, we were interested in exploring the potential of the aforementioned chelating isonitrile ligands in the stabilization of highly reduced iron complexes. We particularly questioned if polynuclear iron complexes with chelating bis(isonitrile) ligands can still be formed, for which to the best of our knowledge no previous examples have been described in the literature.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

et al. 2021

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The divalent iron complexes trans-[FeBr 2 (BINC) 2 ], [Cp*FeCl(BINC)] (Cp* = Me 5 C 5 ), and [FeBr 2 (CNAr 3 NC) 2 ] with the chelating bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr 3 NC (2,2″-diisocyano-3,5,3″,5"tetramethyl-1,1′:3′,1″-terphenyl) have been prepared and characterized. Their subsequent reduction yields the di-and trinuclear compounds [Fe 3 (BINC) 6 ], [Cp*Fe(BINC)] 2 , [Fe(CNAr 3 NC) 2 ] 2 , and [K-(Et 2 O)] 2 [Fe(CNAr 3 NC) 2 ] 2 . The molecular structures of all new species were determined by X-ray crystallography and compared to those of related iron carbonyl complexes, demonstrating that the bidentate isonitrile ligands are capable surrogates for two CO ligands with only minimal distortion of the tetrahedral or octahedral geometry of the parent complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV−vis−NIR spectroelectrochemistry.

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Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

et al. 2021

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“…One can see that an ME medium is definitely lossless, when

ε_{i j}^{normalah} = μ_{i j}^{normalah} = 0

ζ_{i j}^{normalh} = ξ_{i j}^{normalh}

, and

ζ_{i j}^{normalah} = - ξ_{i j}^{normalah}

. These conditions can be rewritten as

…”

Section: The Poynting Theorem In a Me Medium And The Me Fieldsmentioning

confidence: 99%

“…One can see that an ME medium is definitely lossless, when ah ij = ah ij = 0, h ij = h ij , and ah ij = − ah ij . These conditions can be rewritten as [57][58][59]…”

Section: The Poynting Theorem In a Me Medium And The Me Fieldsmentioning

confidence: 99%

Electrodynamics of Magnetoelectric Media and Magnetoelectric Fields

Kamenetskii

2020

Annalen der Physik

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The relationship between magnetoelectricity and electromagnetism is a subject of a strong interest and numerous discussions in microwave and optical wave physics and material sciences. The definition of the energy and momentum of the electromagnetic (EM) field in a magnetoelectric (ME) medium is not a trivial problem. The question of whether electromagnetism and magnetoelectricity can coexist without an extension of Maxwell's theory arises when the effects of EM energy propagation are studied and the group velocity of the waves in an ME medium is considered. The energy balance equation reveals unusual topological structure of fields in ME materials. Together with certain constraints on the constitutive parameters of a medium, definite constraints on the local field structure should be imposed. Analyzing the EM phenomena inside an ME material, the question “what kind of the near fields arising from a sample of such a material can be measured?” should be answered. The visualization of the ME states requires an experimental technique that is based on an effective coupling to the violation of spatial as well as temporal inversion symmetry. To observe the ME energy in a subwavelength region, it is necessary to assume the existence of first‐principle near fields—the ME fields. These are non‐Maxwellian near fields with specific properties of violation of spatial and temporal inversion symmetry. A particular interest to the ME fields arises in studies of metamaterials with “artificial‐atoms” ME elements.

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“…A straightforward strategy to modulate the properties of azulene systems using metal synthons, is the functionalization of the azulene core with coordinating groups that can act as ligands for metal complex formation. In this regard, isocyanides are versatile ligands that form stable organometallic complexes with most transition metals [36,37]. Isocyanide metal complexes are of long-standing importance in catalysis [38], diagnostic medicine [39], and material science [40,41], including liquid crystals [42].…”

Section: Introductionmentioning

confidence: 99%

The 2-isocyanoazulene-gold(I) fragment as a versatile element for organometallic dyes and liquid crystals

et al. 2020

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This manuscript reports the synthesis and liquid crystal behavior of isocyanoazulene gold(I) complexes [AuX(CN-Az)] (Az = azulene; X = halide, perhalophenyl or alkynyl) and [µ-4,4'-C6F4C6F4{Au(CN-Az)}2]. The comparison of the X-ray structures of homologous compounds, reveals that the introduction of a long substituent in the system produces a loss of molecular planarity that induces a decrease in the melting temperatures. The free 2isocyanoazulene is not a liquid crystal itself, but its gold complexes bearing a C10 hydrocarbon chain display a SmA mesophase, whose formation is driven by nanosegregation between molten chains and aromatic parts. The free isocyanide is strongly colored and displays fluorescence in solution associated with the azulene fragment, which is largely diminished upon coordination to the gold fragment.

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Renaissance of Isocyanoarenes as Ligands in Low‐Valent Organometallics

Cited by 13 publications

References 113 publications

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes

Electrodynamics of Magnetoelectric Media and Magnetoelectric Fields

The 2-isocyanoazulene-gold(I) fragment as a versatile element for organometallic dyes and liquid crystals

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