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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...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2018
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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. |
format | Online Article Text |
id | pubmed-6503609 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
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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