Bis(1,5-cyclooctadiene)nickel(0)

Wender, Paul A.; Smith, Thomas E.; Zuo, Gang; Duong, Hung A.; Louie, Janis

doi:10.1002/047084289x.rb118.pub2

Cited by 5 publications

(6 citation statements)

References 379 publications

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“…Last, the identity of the yellow compound could be verified using solution NMR. The 1 H NMR chemical shifts [ 1 H NMR: δ 4.28 (br, CH), 2.05 (br, CH 2 )] are consistent with the literature, as is the 61 Ni chemical shift (δ iso = 936.5 ppm compared to the literature value of 937 ppm). Solution 13 C NMR also indicates the presence of the compound, with the cyclooctadiene ligands observed [ 13 C NMR: δ 89.30 (CH), 30.49 (CH 2 )].…”

Section: Resultssupporting

confidence: 84%

“…Ni(PPh 3 ) 4 and Ni[P(OPh) 3 ] 4 were received as fine powders (red-brown and white, respectively). Two lots of Ni(cod) 2 received had different physical characteristics: the first consisted of olive-gray crystals and was not ground before use or studied in solution because of the mechanochemical sensitivity of the compound; the second consisted of fine yellow crystals consistent with the literature and was ground before use and also characterized by solution NMR spectroscopy. Spectra were collected for stationary powder samples packed under an inert atmosphere in 7-mm-o.d.…”

Section: Methodsmentioning

confidence: 99%

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Structural and Crystallographic Information from ⁶¹Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Werhun

Bryce

2017

Inorg. Chem.

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Despite the significance of nickel compounds, NMR spectroscopy of the active nickel isotope Ni remains a largely unexplored field. While nickel(0) compounds have been studied byNi NMR in solution, solid-state experiments have been limited to Knight shift studies of nickel metal and nickel intermetallics. In conjunction with an NMR study of their ligands and Ni relativistic computations, the firstNi solid-state NMR (SSNMR) spectra of diamagnetic compounds are reported here. Specifically, bis(1,5-cyclooctadiene)nickel(0) [Ni(cod)], tetrakis(triphenylphosphite)nickel(0) [Ni[P(OPh)]], and tetrakis(triphenylphosphine)nickel(0) [Ni(PPh)] were studied. Ni SSNMR spectra of Ni(cod) were used to determine its isotropic chemical shift (δ = 965 ± 10 ppm), span (Ω = 1700 ± 50 ppm), skew (κ = -0.15 ± 0.05), quadrupolar coupling constant (C = 2.0 ± 0.3 MHz), quadrupolar asymmetry parameter (η = 0.5 ± 0.2), and the relative orientation of the chemical shift and electric field gradient tensors. A solution study of Ni(cod) in CD yielded a narrow Ni signal, and the temperature dependence of δ(Ni) was assessed (δ being 936.5 ppm at 295 K). The solution is proposed as a secondary chemical shift reference for Ni NMR in lieu of the extremely toxic Ni(CO) primary reference. For Ni[P(OPh)], Ni SSNMR was used to infer the presence of two distinct crystallographic sites and establish ranges for δ in the solid state, as well as an upper bound for C (3.5 MHz for both sites). For Ni(PPh), line shape fitting provided a δ value of 515 ± 10 ppm, Ω of 50 ± 50 ppm, κ of 0.5 ± 0.5, C of 0.05 ± 0.01 MHz, and η of 0.0 ± 0.2. The study of Ni(PPh), in particular, demonstrates the utility of Ni SSNMR given the lack of a previously reported crystal structure and transient nature of Ni(PPh) in solution.

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Section: Resultssupporting

confidence: 84%

Section: Methodsmentioning

confidence: 99%

Structural and Crystallographic Information from ⁶¹Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Werhun

Bryce

2017

Inorg. Chem.

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“…One of the major reasons for this difference is the relative paucity of suitable Ni 0 precursors. The most frequently used Ni 0 source for both stoichiometric and catalytic reactions is almost certainly commercially available Ni(COD) 2 , which is relatively difficult to prepare and is both air and thermally unstable. Although Ni(COD) 2 is an effective Ni 0 source, it would be useful to have more potential Ni 0 synthons.…”

mentioning

confidence: 99%

Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes

Faller

Hazari

et al. 2012

Organometallics

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Although there are many organic reactions that are catalyzed by either Ni 0 or Pd 0 complexes, in comparison with the case for Pd 0 there has been significantly less work studying coordinatively unsaturated Ni 0 complexes. Here, we develop a simple synthetic route for preparing a number of thermally stable NHC-supported Ni 0 hexadiene complexes in good yield. We examine the stoichiometric reactivity of one of these species and demonstrate that the coordinated hexadiene moiety is labile and can be replaced with a variety of different ligands, including CO, phosphines, isonitriles, and olefins. In addition, we show that the Ni 0 hexadiene complexes are relatively rare examples of homogeneous first-row transition-metal catalysts for the hydrogenation of olefins.

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“…Unfortunately, a reaction starting from model substrate 3a proved this approach does not work and only substrate was identified, which is not surprising, based on the known sensitivity of Ni(cod) 2 . 35…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Directed C–H Functionalization Reactions with a Picolinamide Directing Group: Ni-Catalyzed Cleavage and Byproduct Recycling

et al. 2019

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An efficient strategy for the cleavage of the picolinamide directing group (DG) and recycling of the byproduct generated has been developed. In this protocol, picolinamides were first Boc activated into tertiary N-Boc-N-substituted picolinamides. These were then cleaved via a Ni-catalyzed esterification reaction with EtOH to give valuable N-Boc protected amines. Ni(cod)2 was used as a catalyst without any ligands or base additives. The byproduct, ethyl 2-picolinate can be used to install the picolinamide DG in a direct or indirect manner on amines. The protocol exhibits a broad functional group tolerance and high yields. To demonstrate the utility of this approach, it was applied on many selected examples from the recent C–H functionalization literature featuring 2-picolinamide as a DG.

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Bis(1,5-cyclooctadiene)nickel(0)

Cited by 5 publications

References 379 publications

Structural and Crystallographic Information from ⁶¹Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Structural and Crystallographic Information from ⁶¹Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes

Directed C–H Functionalization Reactions with a Picolinamide Directing Group: Ni-Catalyzed Cleavage and Byproduct Recycling

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Bis(1,5-cyclooctadiene)nickel(0)

Cited by 5 publications

References 379 publications

Structural and Crystallographic Information from 61Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Structural and Crystallographic Information from 61Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes

Directed C–H Functionalization Reactions with a Picolinamide Directing Group: Ni-Catalyzed Cleavage and Byproduct Recycling

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Structural and Crystallographic Information from ⁶¹Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds

Structural and Crystallographic Information from ⁶¹Ni Solid-State NMR Spectroscopy: Diamagnetic Nickel Compounds