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

Changguang Yao; Priyanka Chakraborty; Emanuele Aresu; Huaifeng Li; Chao Guan; Chunhui Zhou; Lan-Chang Liang; Kuo-Wei Huang

doi:10.1039/c8dt03403f

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

Changguang Yao, Priyanka Chakraborty, Emanuele Aresu, Huaifeng Li, Chao Guan, Chunhui Zhou, Lan-Chang Liang, Kuo-Wei Huang

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Abstract

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).

Original language	English (US)
Pages (from-to)	16057-16065
Number of pages	9
Journal	Dalton Transactions
Volume	47
Issue number	45
DOIs	https://doi.org/10.1039/c8dt03403f
State	Published - 2018

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@article{59baae4bd176487d834907e51c3334fe,

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

abstract = "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).",

author = "Changguang Yao and Priyanka Chakraborty and Emanuele Aresu and Huaifeng Li and Chao Guan and Chunhui Zhou and Lan-Chang Liang and Kuo-Wei Huang",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: We acknowledge the financial support from the King Abdullah University of Science and Technology (KAUST) and from the Ministry of Science and Technology of Taiwan (MOST 106-2113-M-110-003).",

year = "2018",

doi = "10.1039/c8dt03403f",

language = "English (US)",

volume = "47",

pages = "16057--16065",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "45",

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TY - JOUR

T1 - Monomeric nickel hydroxide stabilized by a sterically demanding phosphorus–nitrogen PN3P-pincer ligand: synthesis, reactivity and catalysis

AU - Yao, Changguang

AU - Chakraborty, Priyanka

AU - Aresu, Emanuele

AU - Li, Huaifeng

AU - Guan, Chao

AU - Zhou, Chunhui

AU - Liang, Lan-Chang

AU - Huang, Kuo-Wei

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: We acknowledge the financial support from the King Abdullah University of Science and Technology (KAUST) and from the Ministry of Science and Technology of Taiwan (MOST 106-2113-M-110-003).

PY - 2018

Y1 - 2018

N2 - 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).

AB - 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).

UR - http://hdl.handle.net/10754/630582

UR - https://pubs.rsc.org/en/Content/ArticleLanding/2018/DT/C8DT03403F#!divAbstract

UR - http://www.scopus.com/inward/record.url?scp=85056978530&partnerID=8YFLogxK

U2 - 10.1039/c8dt03403f

DO - 10.1039/c8dt03403f

M3 - Article

C2 - 30302466

SN - 1477-9226

VL - 47

SP - 16057

EP - 16065

JO - Dalton Transactions

JF - Dalton Transactions

IS - 45

ER -

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

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CCDC 1817531: Experimental Crystal Structure Determination : hydroxy-{N,N'-(3,3,5-triethylpyridine-2,6(1H,3H)-diylidene)bis[P,P-di-t-butyl(phosphinous amidato)]}-nickel(ii)

CCDC 1817545: Experimental Crystal Structure Determination : [(2,6-dimethylphenyl)carbamothioic S-acidato]-{N,N'-(3,3,5-triethylpyridine-2,6(1H,3H)-diylidene)bis[P,P-di-t-butyl(phosphinous amidato)]}-nickel(ii)

CCDC 1834798: Experimental Crystal Structure Determination : (benzamidato)-{N,N'-(3,3,5-triethylpyridine-2,6(1H,3H)-diylidene)bis[P,P-di-t-butyl(phosphinous amidato)]}-nickel(ii)

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

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CCDC 1817531: Experimental Crystal Structure Determination : hydroxy-{N,N'-(3,3,5-triethylpyridine-2,6(1H,3H)-diylidene)bis[P,P-di-t-butyl(phosphinous amidato)]}-nickel(ii)

CCDC 1817545: Experimental Crystal Structure Determination : [(2,6-dimethylphenyl)carbamothioic S-acidato]-{N,N'-(3,3,5-triethylpyridine-2,6(1H,3H)-diylidene)bis[P,P-di-t-butyl(phosphinous amidato)]}-nickel(ii)

CCDC 1834798: Experimental Crystal Structure Determination : (benzamidato)-{N,N'-(3,3,5-triethylpyridine-2,6(1H,3H)-diylidene)bis[P,P-di-t-butyl(phosphinous amidato)]}-nickel(ii)

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