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Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)

[Image: see text] The unique synthesis and reactivity of [((R)PNP*)NiH] complexes (1a,b), based on metal–ligand cooperation (MLC), are presented ((R)PNP* = deprotonated PNP ligand, R = (i)Pr, (t)Bu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes...

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Autores principales: Oren, Dror, Diskin-Posner, Yael, Avram, Liat, Feller, Moran, Milstein, David
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6503609/
https://www.ncbi.nlm.nih.gov/pubmed/31080304
http://dx.doi.org/10.1021/acs.organomet.8b00160
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author Oren, Dror
Diskin-Posner, Yael
Avram, Liat
Feller, Moran
Milstein, David
author_facet Oren, Dror
Diskin-Posner, Yael
Avram, Liat
Feller, Moran
Milstein, David
author_sort Oren, Dror
collection PubMed
description [Image: see text] The unique synthesis and reactivity of [((R)PNP*)NiH] complexes (1a,b), based on metal–ligand cooperation (MLC), are presented ((R)PNP* = deprotonated PNP ligand, R = (i)Pr, (t)Bu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [((R)PNP)Ni(MeCN)](BF(4))(2) with sodium amalgam or by reaction of the free ligand with Ni(0)(COD)(2). Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO(2) via MLC to form a rare example of η(1) binding of CO(2) to nickel, complexes 4a,b. An unusual CO(2) cleavage process by complex 4b, involving C–O and C–P cleavage and C–C bond formation, led to the Ni–CO complex 3b and to the new complex [(P(i)Pr(2)NC(2)O(2))Ni(P(O)(i)Pr(2))] (5b). All complexes have been fully characterized by NMR and X-ray crystallography.
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spelling pubmed-65036092019-05-08 Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2) Oren, Dror Diskin-Posner, Yael Avram, Liat Feller, Moran Milstein, David Organometallics [Image: see text] The unique synthesis and reactivity of [((R)PNP*)NiH] complexes (1a,b), based on metal–ligand cooperation (MLC), are presented ((R)PNP* = deprotonated PNP ligand, R = (i)Pr, (t)Bu). Unexpectedly, the dearomatized complexes 1a,b were obtained by reduction of the dicationic complexes [((R)PNP)Ni(MeCN)](BF(4))(2) with sodium amalgam or by reaction of the free ligand with Ni(0)(COD)(2). Complex 1b reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex 3b. Complexes 1a,b also react with CO(2) via MLC to form a rare example of η(1) binding of CO(2) to nickel, complexes 4a,b. An unusual CO(2) cleavage process by complex 4b, involving C–O and C–P cleavage and C–C bond formation, led to the Ni–CO complex 3b and to the new complex [(P(i)Pr(2)NC(2)O(2))Ni(P(O)(i)Pr(2))] (5b). All complexes have been fully characterized by NMR and X-ray crystallography. American Chemical Society 2018-05-09 2018-07-23 /pmc/articles/PMC6503609/ /pubmed/31080304 http://dx.doi.org/10.1021/acs.organomet.8b00160 Text en Copyright © 2018 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Oren, Dror
Diskin-Posner, Yael
Avram, Liat
Feller, Moran
Milstein, David
Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)
title Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)
title_full Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)
title_fullStr Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)
title_full_unstemmed Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)
title_short Metal–Ligand Cooperation as Key in Formation of Dearomatized Ni(II)–H Pincer Complexes and in Their Reactivity toward CO and CO(2)
title_sort metal–ligand cooperation as key in formation of dearomatized ni(ii)–h pincer complexes and in their reactivity toward co and co(2)
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6503609/
https://www.ncbi.nlm.nih.gov/pubmed/31080304
http://dx.doi.org/10.1021/acs.organomet.8b00160
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