2-Pyridyl-phosphine and -diphosphine complexes of nickel(0), their reactivity (including aqueous solution chemistry), and some related, incidental methylphosphonium iodides

Page, Matthew D. Le; Patrick, Brian O.; Rettig, Steven J.; James, Brian R.

doi:10.1016/j.ica.2015.04.003

Cited by 6 publications

(3 citation statements)

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“…The formation of these species were confirmed by omitting ketene from the reactions, which led to identical 31 P{ 1 H} NMR spectra. Furthermore, in the reaction with dppe, only a broad singlet at 44.6 ppm, which is consistent with (dppe) 2 Ni, was observed . The formation of bis-chelated species is detrimental to Ni–ketene complex formation because for every L 2 Ni species, an equivalent of Ni(COD) 2 is left over which reacts rapidly with ketene to form nickel carbonyl compounds …”

Section: Resultssupporting

confidence: 59%

“…Furthermore, in the reaction with dppe, only a broad singlet at 44.6 ppm, which is consistent with (dppe) 2 Ni, was observed. 16 The formation of bis-chelated species is detrimental to Ni−ketene complex formation because for every L 2 Ni species, an equivalent of Ni(COD) 2 is left over which reacts rapidly with ketene to form nickel carbonyl compounds. 8 Gratifyingly, the reaction between dppf and Ni(COD) 2 formed (dppf)Ni(COD) quantitatively, observed as a sole singlet at 34 ppm in the 31 P{ 1 H} NMR spectrum; (dppf) 2 Ni was not observed.…”

Section: ■ Resultsmentioning

confidence: 99%

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Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel–Ketene Complexes

2016

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A series of (dppf)Ni(ketene) complexes were synthesized and fully characterized. In the solid state, the complexes possess η-(C,O) coordination of the ketene in an overall planar configuration. They display similar structure in solution, except in some cases, the η-(C,C) coordination mode is also detected. A combination of kinetic analysis and DFT calculations reveals the complexes undergo thermal decomposition by isomerization from η-(C,O) to η-(C,C) followed by scission of the C═C bond, which is usually rate limiting and results in an intermediate carbonyl carbene complex. Subsequent rearrangement of the carbene ligand is rate limiting for electron poor and sterically large ketenes, and results in a carbonyl alkene complex. The alkene readily dissociates, affording alkenes and (dppf)Ni(CO). Computational modeling of the decarbonylation pathway with partial phosphine dissociation reveals the barrier is reduced significantly, explaining the instability of ketene complexes with monodentate phosphines.

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Section: Resultssupporting

confidence: 59%

Section: ■ Resultsmentioning

confidence: 99%

Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel–Ketene Complexes

2016

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“…The molecular structure of (dppbz)Ni(PMe 3 ) 2 has been determined by X-ray diffraction, as illustrated in Figure . As expected for a d 10 metal center, the structure of (dppbz)Ni(PMe 3 ) 2 is based on a tetrahedral geometry, with the [(dppbz)Ni] chelate ring adopting an almost orthogonal conformation to the [Ni(PMe 3 ) 2 ] plane with a dihedral angle of 89.3°.…”

Section: Results and Discussionmentioning

confidence: 92%

Zerovalent Nickel Compounds Supported by 1,2-Bis(diphenylphosphino)benzene: Synthesis, Structures, and Catalytic Properties

2017

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Zerovalent nickel compounds which feature 1,2-bis(diphenylphosphino)benzene (dppbz) were obtained via the reactivity of dppbz towards Ni(PMe), which affords sequentially (dppbz)Ni(PMe) and Ni(dppbz). Furthermore, the carbonyl derivatives (dppbz)Ni(PMe)(CO) and (dppbz)Ni(CO) may be obtained via the reaction of CO with (dppbz)Ni(PMe). Other methods for the synthesis of these carbonyl compounds include (i) the formation of (dppbz)Ni(CO) by the reaction of Ni(PPh)(CO) with dppbz and (ii) the formation of (dppbz)Ni(PMe)(CO) by the reaction of (dppbz)Ni(CO) with PMe. Comparison of the ν(CO) IR spectroscopic data for (dppbz)Ni(CO) with other (diphosphine)Ni(CO) compounds provides a means to evaluate the electronic nature of dppbz. Specifically, comparison with (dppe)Ni(CO) indicates that the o-phenylene linker creates a slightly less electron donating ligand than does an ethylene linker. The steric impact of the dppbz ligand in relation to other diphosphine ligands has also been evaluated in terms of its buried volume (%V) and steric maps. The nickel center of (dppbz)Ni(PMe) may be protonated by formic acid at room temperature to afford [(dppbz)Ni(PMe)H], but at elevated temperatures, effects catalytic release of H from formic acid. Analogous studies with Ni(dppbz) and Ni(PMe) indicate that the ability to protonate the nickel centers in these compounds increases in the sequence Ni(dppbz) < (dppbz)Ni(PMe) < Ni(PMe); correspondingly, the pK values of the protonated derivatives increase in the sequence [Ni(dppbz)H] < [(dppbz)Ni(PMe)H] < [Ni(PMe)H]. (dppbz)Ni(PMe) and Ni(PMe) also serve as catalysts for the formation of alkoxysilanes by (i) hydrosilylation of PhCHO by PhSiH and PhSiH and (ii) dehydrocoupling of PhCHOH with PhSiH and PhSiH.

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1,3-P,N hybrid ligands in mononuclear coordination chemistry and homogeneous catalysis

Rong

Holtrop

Slootweg

et al. 2019

Coordination Chemistry Reviews

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2-Pyridyl-phosphine and -diphosphine complexes of nickel(0), their reactivity (including aqueous solution chemistry), and some related, incidental methylphosphonium iodides

Cited by 6 publications

References 58 publications

Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel–Ketene Complexes

Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel–Ketene Complexes

Zerovalent Nickel Compounds Supported by 1,2-Bis(diphenylphosphino)benzene: Synthesis, Structures, and Catalytic Properties

1,3-P,N hybrid ligands in mononuclear coordination chemistry and homogeneous catalysis

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