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[Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes

The addition of PPh(2)H, PPhMeH, PPhH(2), P(para‐Tol)H(2), PMesH(2) and PH(3) to the two‐coordinate Ni(0) N‐heterocyclic carbene species [Ni(NHC)(2)] (NHC=IiPr(2), IMe(4), IEt(2)Me(2)) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these...

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Autores principales: Sabater, Sara, Schmidt, David, Schmidt, Heidi (née Schneider), Kuntze‐Fechner, Maximilian W., Zell, Thomas, Isaac, Connie J., Rajabi, Nasir A., Grieve, Harry, Blackaby, William J. M., Lowe, John P., Macgregor, Stuart A., Mahon, Mary F., Radius, Udo, Whittlesey, Michael K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8518396/
https://www.ncbi.nlm.nih.gov/pubmed/34190374
http://dx.doi.org/10.1002/chem.202101484
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author Sabater, Sara
Schmidt, David
Schmidt, Heidi (née Schneider)
Kuntze‐Fechner, Maximilian W.
Zell, Thomas
Isaac, Connie J.
Rajabi, Nasir A.
Grieve, Harry
Blackaby, William J. M.
Lowe, John P.
Macgregor, Stuart A.
Mahon, Mary F.
Radius, Udo
Whittlesey, Michael K.
author_facet Sabater, Sara
Schmidt, David
Schmidt, Heidi (née Schneider)
Kuntze‐Fechner, Maximilian W.
Zell, Thomas
Isaac, Connie J.
Rajabi, Nasir A.
Grieve, Harry
Blackaby, William J. M.
Lowe, John P.
Macgregor, Stuart A.
Mahon, Mary F.
Radius, Udo
Whittlesey, Michael K.
author_sort Sabater, Sara
collection PubMed
description The addition of PPh(2)H, PPhMeH, PPhH(2), P(para‐Tol)H(2), PMesH(2) and PH(3) to the two‐coordinate Ni(0) N‐heterocyclic carbene species [Ni(NHC)(2)] (NHC=IiPr(2), IMe(4), IEt(2)Me(2)) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [H−Ni−PR(2)] or novel trans [R(2)P−Ni−PR(2)] geometries. The bis‐phosphido complexes are more accessible when smaller NHCs (IMe(4)>IEt(2)Me(2)>IiPr(2)) and phosphines are employed. P−P activation of the diphosphines R(2)P−PR(2) (R(2)=Ph(2), PhMe) provides an alternative route to some of the [Ni(NHC)(2)(PR(2))(2)] complexes. DFT calculations capture these trends with P−H bond activation proceeding from unconventional phosphine adducts in which the H substituent bridges the Ni−P bond. P−P bond activation from [Ni(NHC)(2)(Ph(2)P−PPh(2))] adducts proceeds with computed barriers below 10 kcal mol(−1). The ability of the [Ni(NHC)(2)] moiety to afford isolable terminal phosphido products reflects the stability of the Ni−NHC bond that prevents ligand dissociation and onward reaction.
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spelling pubmed-85183962021-10-21 [Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes Sabater, Sara Schmidt, David Schmidt, Heidi (née Schneider) Kuntze‐Fechner, Maximilian W. Zell, Thomas Isaac, Connie J. Rajabi, Nasir A. Grieve, Harry Blackaby, William J. M. Lowe, John P. Macgregor, Stuart A. Mahon, Mary F. Radius, Udo Whittlesey, Michael K. Chemistry Full Papers The addition of PPh(2)H, PPhMeH, PPhH(2), P(para‐Tol)H(2), PMesH(2) and PH(3) to the two‐coordinate Ni(0) N‐heterocyclic carbene species [Ni(NHC)(2)] (NHC=IiPr(2), IMe(4), IEt(2)Me(2)) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [H−Ni−PR(2)] or novel trans [R(2)P−Ni−PR(2)] geometries. The bis‐phosphido complexes are more accessible when smaller NHCs (IMe(4)>IEt(2)Me(2)>IiPr(2)) and phosphines are employed. P−P activation of the diphosphines R(2)P−PR(2) (R(2)=Ph(2), PhMe) provides an alternative route to some of the [Ni(NHC)(2)(PR(2))(2)] complexes. DFT calculations capture these trends with P−H bond activation proceeding from unconventional phosphine adducts in which the H substituent bridges the Ni−P bond. P−P bond activation from [Ni(NHC)(2)(Ph(2)P−PPh(2))] adducts proceeds with computed barriers below 10 kcal mol(−1). The ability of the [Ni(NHC)(2)] moiety to afford isolable terminal phosphido products reflects the stability of the Ni−NHC bond that prevents ligand dissociation and onward reaction. John Wiley and Sons Inc. 2021-08-04 2021-09-15 /pmc/articles/PMC8518396/ /pubmed/34190374 http://dx.doi.org/10.1002/chem.202101484 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Sabater, Sara
Schmidt, David
Schmidt, Heidi (née Schneider)
Kuntze‐Fechner, Maximilian W.
Zell, Thomas
Isaac, Connie J.
Rajabi, Nasir A.
Grieve, Harry
Blackaby, William J. M.
Lowe, John P.
Macgregor, Stuart A.
Mahon, Mary F.
Radius, Udo
Whittlesey, Michael K.
[Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes
title [Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes
title_full [Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes
title_fullStr [Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes
title_full_unstemmed [Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes
title_short [Ni(NHC)(2)] as a Scaffold for Structurally Characterized trans [H−Ni−PR(2)] and trans [R(2)P−Ni−PR(2)] Complexes
title_sort [ni(nhc)(2)] as a scaffold for structurally characterized trans [h−ni−pr(2)] and trans [r(2)p−ni−pr(2)] complexes
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8518396/
https://www.ncbi.nlm.nih.gov/pubmed/34190374
http://dx.doi.org/10.1002/chem.202101484
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