Monomeric nickel hydroxide stabilized by a sterically demanding phosphorus–nitrogen PN3P-pincer ligand: synthesis, reactivity and catalysis

A terminal nickel hydroxide complex (PN3P)Ni(OH) (3) bearing the 2nd generation phosphorus–nitrogen PN3P-pincer ligand has been synthesized and structurally characterized. As a nucleophile, 3 reacts with CO to afford the hydroxycarbonyl complex 4, (PN3P)Ni(COOH). 3 can also activate CO2 and CS2 to p...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 47; no. 45; pp. 16057 - 16065
Main Authors Yao, Changguang, Chakraborty, Priyanka, Aresu, Emanuele, Li, Huaifeng, Guan, Chao, Zhou, Chunhui, Lan-Chang, Liang, Kuo-Wei, Huang
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 01.01.2018
Subjects
Amides
Aromatic compounds
Bicarbonates
Bimetals
Catalysis
Chemical synthesis
Crystallography
Isocyanates
Ligands
Nickel
Nickel compounds
NMR
Nuclear magnetic resonance
Phosphorus
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Summary:A terminal nickel hydroxide complex (PN3P)Ni(OH) (3) bearing the 2nd generation phosphorus–nitrogen PN3P-pincer ligand has been synthesized and structurally characterized. As a nucleophile, 3 reacts with CO to afford the hydroxycarbonyl complex 4, (PN3P)Ni(COOH). 3 can also activate CO2 and CS2 to produce nickel bicarbonate (PN3P)Ni(OCOOH) (5) and bimetallic dithiocarbonate [(PN3P)NiS]2CO (6) respectively, as well as to promote aryl isocyanate and isothiocyanate insertion into the Ni–OH bond to give the corresponding (PN3P)NiEC(O)NHAr complexes (E = O, 7; E = S, 8). In addition, 3 catalyzes the nitrile hydration to various amides with well-defined intermediates (PN3P)Ni–NHC(O)R (R = Me, 9; R = Ph, 10).
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ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt03403f