Synthesis and structural investigation of mono- and dimetallic N-heterocyclic carbene complexes of group VII transition metals

Fraser, Roan; Sittert, Cornelia Gertina Catharina Elizabeth van; Rooyen, Petrus H. van; Landman, Marilé

doi:10.1016/j.jorganchem.2017.02.031

Cited by 18 publications

(2 citation statements)

References 48 publications

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“…2 The NHC complexes have been considered for numerous applications in various areas such as organometallic drugs, 3 in the industry as catalysts for organic alterations and polymerization reactions, in dye-sensitized thin-lm solar cells and in thousands of antimicrobials and anti-tumor medicines. 4 Since then, the synthesis of novel NH-free carbene ligands and their corresponding metallic compounds such as with silver and selenium have become an area of extensive research. 5 Various researches have shown that protein-rich foods such as eggs, sh and meat also contain huge amounts of selenium, with its antioxidant activity through enzymes such as glutathione peroxidase.…”

Section: Introductionmentioning

confidence: 99%

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Characterization of three different benzimidazolium ligands and their organo-selenium complexes by using density functional theory and Raman spectroscopy

Younas,

Riaz,

Nawaz

et al. 2023

RSC Adv.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Characterization of three different benzimidazolium ligands and their organo-selenium complexes by using density functional theory and Raman spectroscopy

Younas,

Riaz,

Nawaz

et al. 2023

RSC Adv.

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Regiochemistry Control by Bipyridine Substituents in the Deprotonation of Re^I and Mo^IIN‐Alkylimidazole Complexes

Espinal‐Viguri

Fombona

Álvarez

et al. 2019

Chemistry A European J

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Compounds containing N‐alkylimidazoles (N‐RIm) and 4,4′‐disubstituted 2,2′‐bipyridines (4,4′‐R′2bipy) coordinated to cationic {Mo(η3‐C4H7)(CO)2} and {Re(CO)3} fragments undergo deprotonation of the C2‐H group of the N‐RIm ligands in their reactions with KN(SiMe3)2. The resulting internal nucleophile adds either to one pyridyl ring, which becomes dearomatized and can undergo ring opening in the subsequent reaction with excess MeOTf, or to the metal center, yielding imidazol‐2‐yl complexes, which in turn add HOTf or MeOTf, affording N‐heterocyclic carbene complexes. Which pathway is followed is dictated by the metal and the nature of the imidazole (R) and bipyridine (R′) substituents. For ReI compounds, addition to pyridine is found with R′=tBu and OMe, whereas for R=Me and R′=NMe2, imidazolyl formation is preferred. Coordination of 4,7‐Cl2‐1,10‐phenanthroline to MoII favors C−C coupling, in contrast to the analogous parent bipy or phenanthroline complexes, for which formation of the imidazol‐2‐yl complexes had been found. DFT calculations showed the theoretically expected products in each case, and following their predictions new types of products were obtained experimentally.

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N‐Heterocyclic Silylenes as Ligands in Transition Metal Carbonyl Chemistry: Nature of Their Bonding and Supposed Innocence

Krahfuß

Nitsch

Bickelhaupt

et al. 2020

Chemistry A European J

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A study on the reactivity of the N‐heterocyclic silylene Dipp2NHSi (1,3‐bis(diisopropylphenyl)‐1,3‐diaza‐2‐silacyclopent‐4‐en‐2‐yliden) with the transition metal complexes [Ni(CO)4], [M(CO)6] (M=Cr, Mo, W), [Mn(CO)5(Br)] and [(η5‐C5H5)Fe(CO)2(I)] is reported. We demonstrate that N‐heterocyclic silylenes, the higher homologues of the now ubiquitous NHC ligands, show a remarkably different behavior in coordination chemistry compared to NHC ligands. Calculations on the electronic features of these ligands revealed significant differences in the frontier orbital region which lead to some peculiarities of the coordination chemistry of silylenes, as demonstrated by the synthesis of the dinuclear, NHSi‐bridged complex [{Ni(CO)2(μ‐Dipp2NHSi)}2] (2), complexes [M(CO)5(Dipp2NHSi)] (M=Cr 3, Mo 4, W 5), [Mn(CO)3(Dipp2NHSi)2(Br)] (9) and [(η5‐C5H5)Fe(CO)2(Dipp2NHSi‐I)] (10). DFT calculations on several model systems [Ni(L)], [Ni(CO)3(L)], and [W(CO)5(L)] (L=NHC, NHSi) reveal that carbenes are typically the much better donor ligands with a larger intrinsic strength of the metal–ligand bond. The decrease going from the carbene to the silylene ligand is mainly caused by favorable electrostatic contributions for the NHC ligand to the total bond strength, whereas the orbital interactions were often found to be higher for the silylene complexes. Furthermore, we have demonstrated that the contribution of σ‐ and π‐interaction depends significantly on the system under investigation. The σ‐interaction is often much weaker for the NHSi ligand compared to NHC but, interestingly, the π‐interaction prevails for many NHSi complexes. For the carbonyl complexes, the NHSi ligand is the better σ‐donor ligand, and contributions of π‐symmetry play only a minor role for the NHC and NHSi co‐ligands.

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Synthesis and structural investigation of mono- and dimetallic N-heterocyclic carbene complexes of group VII transition metals

Cited by 18 publications

References 48 publications

Characterization of three different benzimidazolium ligands and their organo-selenium complexes by using density functional theory and Raman spectroscopy

Characterization of three different benzimidazolium ligands and their organo-selenium complexes by using density functional theory and Raman spectroscopy

Regiochemistry Control by Bipyridine Substituents in the Deprotonation of Re^I and Mo^IIN‐Alkylimidazole Complexes

N‐Heterocyclic Silylenes as Ligands in Transition Metal Carbonyl Chemistry: Nature of Their Bonding and Supposed Innocence

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Synthesis and structural investigation of mono- and dimetallic N-heterocyclic carbene complexes of group VII transition metals

Cited by 18 publications

References 48 publications

Characterization of three different benzimidazolium ligands and their organo-selenium complexes by using density functional theory and Raman spectroscopy

Characterization of three different benzimidazolium ligands and their organo-selenium complexes by using density functional theory and Raman spectroscopy

Regiochemistry Control by Bipyridine Substituents in the Deprotonation of ReI and MoIIN‐Alkylimidazole Complexes

N‐Heterocyclic Silylenes as Ligands in Transition Metal Carbonyl Chemistry: Nature of Their Bonding and Supposed Innocence

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Regiochemistry Control by Bipyridine Substituents in the Deprotonation of Re^I and Mo^IIN‐Alkylimidazole Complexes