Nickel Tetracarbonyl as Starting Material for the Synthesis of NHC‐stabilized Nickel(II) Allyl Complexes

Berthel, Johannes H. J.; Krahfuß, Mirjam J.; Radius, Udo

doi:10.1002/zaac.201900326

Cited by 7 publications

(3 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1.952(2) Å), they differ significantly in the trans isomer 2a- cis (Ni–C(NHC) 1.905 Å vs Ni–C(neosilyl) 2.032 Å). These metric values are in good agreement with other structurally characterized Ni-NHC complexes ,,− and can be attributed to the different trans-influence of alkyl and NHC ligands, respectively.…”

Section: Resultssupporting

confidence: 89%

Ligand Exchange Reactions of [(tmeda)NiR₂] (R = CH₂CMe₃, CH₂SiMe₃, CH₂CMe₂Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

et al. 2020

View full text Add to dashboard Cite

Bis(alkyl)nickel(II) complexes [(tmeda)NiR2] (R = CH2SiMe3 (1a), CH2CMe3 (1b), CH2CMe2Ph (1c)) can be prepared from [(tmeda)Ni(acac)2] and MgR2. This approach is equivalent to and, in some cases, even superior to the frequently employed reaction of [(py)4NiR2] with Grignard reagents. With [(tmeda)NiR2] as the starting material, ligand exchange reactions with N-heterocyclic carbenes and bidentate phosphines were explored. The reaction of [(tmeda)NiR2] with IiPr2Me2 (IiPr2Me = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) yields three different classes of products: (a) [cis-(IiPr2Me2)2Ni(CH2SiMe3)2] (2a- cis ) derived from NHC by tmeda replacement, (b) [(IiPr2Me2)(κ-C:C-IiPr2MeCH2)Ni(CH2SiMe3)] (3a) as a result of C–H bond activation of one iPr group of the NHC ligand, and (c) [cis-(IiPr2Me2)2Ni(κ-C:C-CH2CMe2C6H4)] (4c- cis ), in which an o-C–H bond of the neophyl ligand has been activated. Addition of depe (depe = Et2PCH2CH2PEt2) to 1a,c results in a clean tmeda replacement to give the corresponding complexes [(dppe)NiR2] (R = CH2SiMe3 (5a), CH2CMe2Ph (5c)). All compounds have been fully characterized by various spectroscopic methods and in most cases by single-crystal X-ray diffraction.

show abstract

Section: Resultssupporting

confidence: 89%

Ligand Exchange Reactions of [(tmeda)NiR₂] (R = CH₂CMe₃, CH₂SiMe₃, CH₂CMe₂Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Consequently, we conducted a detailed variable-temperature 1 H NMR study between 245 and 330 K in 5 K increments (Figure S12). The coalescence temperature was found to be 270 K, which gives a calculated rotation energy barrier for the isopropyl moiety of 12.4 kcal/mol. , Finally, the carbene resonance for 3 is observed in the 13 C NMR at 197.68 ppm (Figure S9).…”

Section: Results and Discussionmentioning

confidence: 97%

“…The coalescence temperature was found to be 270 K, which gives a calculated rotation energy barrier for the isopropyl moiety of 12.4 kcal/mol. 67,68 Finally, the carbene resonance for 3 is observed in the 13 C NMR at 197.68 ppm (Figure S9).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of d¹⁰ N-Heterocyclic Carbene Complexes with a Perimidine Scaffold

Strausser

Jenkins

2021

Organometallics

View full text Add to dashboard Cite

N-Heterocyclic carbenes (NHCs) are vital auxiliary ligands for organometallic chemistry, and although many variants have been synthesized, by far the most common are based on fivemembered rings, such as imidazole or benzimidazole. Unlike NHC complexes built on five-membered rings, which are typically conjugated, exploration of six-membered-ring NHC variants has focused on nonconjugated versions, such as N,N′-diamidocarbenes. Reports of conjugated six-membered ring NHCs are limited to metal complexes with a perimidine scaffold that are in a narrow range of between six and eight d electrons (on metals from groups 8−10). This manuscript showcases the synthesis of four d 10 metal complexes with a perimidine scaffold. The gold and silver complexes have a linear geometry, while the copper and platinum complexes are three-coordinated. All complexes were characterized by single-crystal X-ray crystallography, multinuclear NMR, and additional spectroscopic methods.

show abstract

On the Reactivity of a NHC Nickel Bis‐Boryl Complex: Reductive Elimination and Formation of Mono‐Boryl Complexes

Tendera

Kuehn

Marder

et al. 2023

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The synthesis of the first terminal mono‐boryl complexes of nickel, which are not stabilized by a pincer ligand, is reported. The reaction of the nickel bis‐boryl complex cis‐[Ni(iPr2ImMe)2(Bcat)2] 1 (cat = 1,2‐O2C6H4) with the small donor ligand PMe3 led to a complete ligand exchange at nickel with reductive elimination of B2cat2, formation of the bisNHC adduct [B2cat2 · (iPr2ImMe)2] 3 and formation of [Ni(PMe3)4] 2 as the metal‐containing species. Electrophilic attack of MeI on complex 1 or ligand dismutation of 1 with trans[Ni(iPr2ImMe)2Br2] led to loss of only one boryl ligand of 1 and afforded the nickel mono‐boryl complexes trans‐[Ni(iPr2ImMe)2(Bcat)Br] 4a and trans‐[Ni(iPr2ImMe)2(Bcat)I] 4b.

show abstract

Nickel Tetracarbonyl as Starting Material for the Synthesis of NHC‐stabilized Nickel(II) Allyl Complexes

Cited by 7 publications

References 52 publications

Ligand Exchange Reactions of [(tmeda)NiR₂] (R = CH₂CMe₃, CH₂SiMe₃, CH₂CMe₂Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

Ligand Exchange Reactions of [(tmeda)NiR₂] (R = CH₂CMe₃, CH₂SiMe₃, CH₂CMe₂Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

Synthesis of d¹⁰ N-Heterocyclic Carbene Complexes with a Perimidine Scaffold

On the Reactivity of a NHC Nickel Bis‐Boryl Complex: Reductive Elimination and Formation of Mono‐Boryl Complexes

Contact Info

Product

Resources

About

Nickel Tetracarbonyl as Starting Material for the Synthesis of NHC‐stabilized Nickel(II) Allyl Complexes

Cited by 7 publications

References 52 publications

Ligand Exchange Reactions of [(tmeda)NiR2] (R = CH2CMe3, CH2SiMe3, CH2CMe2Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

Ligand Exchange Reactions of [(tmeda)NiR2] (R = CH2CMe3, CH2SiMe3, CH2CMe2Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

Synthesis of d10 N-Heterocyclic Carbene Complexes with a Perimidine Scaffold

On the Reactivity of a NHC Nickel Bis‐Boryl Complex: Reductive Elimination and Formation of Mono‐Boryl Complexes

Contact Info

Product

Resources

About

Ligand Exchange Reactions of [(tmeda)NiR₂] (R = CH₂CMe₃, CH₂SiMe₃, CH₂CMe₂Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

Ligand Exchange Reactions of [(tmeda)NiR₂] (R = CH₂CMe₃, CH₂SiMe₃, CH₂CMe₂Ph) with N-Heterocyclic Carbenes and Bidentate Phosphines

Synthesis of d¹⁰ N-Heterocyclic Carbene Complexes with a Perimidine Scaffold