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In the literature selectivity was often defined as a simple ratio between Markovnikov and anti-Markovnikov products (Scheme1), while the other by-products are neglected. Although such calculations gave higher selectivity values, catalyst optimization resulted in lower isolated yields due to formation of other by-products. Throughout the present study the material balance on phosphorus species was verified in each experiment (the product, unreacted H-phosphonate and overall amount of by-products)
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In the literature selectivity was often defined as a simple ratio between Markovnikov and anti-Markovnikov products (Scheme1), while the other by-products are neglected. Although such calculations gave higher selectivity values, catalyst optimization resulted in lower isolated yields due to formation of other by-products. Throughout the present study the material balance on phosphorus species was verified in each experiment (the product, unreacted H-phosphonate and overall amount of by-products).
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Nickel complexes are known to catalyze alkyne polymerization
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[22])
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78649533445
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31PNMR (DMSO): δ=56.3, 30.4, 30.2, -13.9, -14.2
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31PNMR (DMSO): δ=56.3, 30.4, 30.2, -13.9, -14.2.
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Formation of a broad signal is an indication of complexation to the metal center (or exchange), see
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Formation of a broad signal is an indication of complexation to the metal center (or exchange), see
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In the present study we did not investigate the influence of the metal salt on by-products formation, since in the optimized conditions high product yields were obtained
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In the present study we did not investigate the influence of the metal salt on by-products formation, since in the optimized conditions high product yields were obtained.
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External nucleophilic attack is more common for π-complexes of divalent metal derivatives, although involvement of π-complexes of zero-valent metal derivatives can not be excluded. In the studied system Ni(II) and Ni(0) centers can be readily interconverted by oxidative addition/reductive elimination of the P-H bond (in Scheme3 ligands on Ni are omitted for clarity)
-
External nucleophilic attack is more common for π-complexes of divalent metal derivatives, although involvement of π-complexes of zero-valent metal derivatives can not be excluded. In the studied system Ni(II) and Ni(0) centers can be readily interconverted by oxidative addition/reductive elimination of the P-H bond (in Scheme3 ligands on Ni are omitted for clarity).
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[12,16,18])
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[12,16,18]).
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[12,16-18]), for the calculations here the simple model with X=H was utilized
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[12,16-18]), for the calculations here the simple model with X=H was utilized.
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At the moment it is not possible to unambiguously rule out either of the pathways due to known limitations of calculation accuracy. See the reviews for a discussion of the accuracy of density functional calculations for studying reaction mechanisms of transition metal-catalyzed transformations
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n species are generated by ligand exchange reaction (see Scheme3 and related discussion)
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n species are generated by ligand exchange reaction (see Scheme3 and related discussion).
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