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Tytuł:
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Atypical and Asymmetric 1,3-P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes.
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Autorzy:
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Rong MK; Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Holtrop F; Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Bobylev EO; Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Nieger M; Department of Chemistry, University of Helsinki, A. I. Virtasen aukio 1, P.O. Box 55, FIN-00014, Helsinki, Finland.
Ehlers AW; Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.; Department of Chemistry, University of Johannesburg, Oakland Park, 2006, Johannesburg, South Africa.; Present address: Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, P.O. Box 94157, 1090 GD, Amsterdam, The Netherlands.
Slootweg JC; Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.; Present address: Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, P.O. Box 94157, 1090 GD, Amsterdam, The Netherlands.
Lammertsma K; Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.; Department of Chemistry, University of Johannesburg, Oakland Park, 2006, Johannesburg, South Africa.
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Źródło:
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Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Oct 07; Vol. 27 (56), pp. 14007-14016. Date of Electronic Publication: 2021 Sep 08.
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Typ publikacji:
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Journal Article
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Język:
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English
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Imprint Name(s):
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Original Publication: Weinheim, Germany : Wiley-VCH
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MeSH Terms:
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Ligands*
Catalysis
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References:
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Chemistry. 2009 Jul 20;15(29):7167-79. (PMID: 19544504)
Dalton Trans. 2019 Feb 5;48(6):1936-1940. (PMID: 30574977)
Org Biomol Chem. 2017 Dec 13;15(48):10134-10144. (PMID: 29188244)
Chem Commun (Camb). 2016 May 7;52(37):6288-91. (PMID: 27086679)
J Org Chem. 2006 Apr 28;71(9):3375-80. (PMID: 16626116)
J Am Chem Soc. 2004 Mar 24;126(11):3412-3. (PMID: 15025454)
Chem Rev. 1998 Apr 2;98(2):409-548. (PMID: 11848906)
Chem Commun (Camb). 2016 Jan 28;52(8):1685-8. (PMID: 26660087)
Angew Chem Int Ed Engl. 2013 Oct 25;52(44):11589-93. (PMID: 24038711)
Organometallics. 2017 Mar 13;36(5):1079-1090. (PMID: 28316361)
Angew Chem Int Ed Engl. 2008;47(10):1814-8. (PMID: 18236495)
J Am Chem Soc. 2012 Jan 11;134(1):201-4. (PMID: 22185581)
Chemistry. 2021 Oct 7;27(56):14007-14016. (PMID: 34403555)
J Am Chem Soc. 2006 Jan 18;128(2):438-53. (PMID: 16402830)
Chem Soc Rev. 2016 Feb 21;45(4):775-88. (PMID: 26255747)
Chemistry. 2015 Jun 22;21(26):9328-31. (PMID: 25980531)
Phys Chem Chem Phys. 2008 Nov 28;10(44):6615-20. (PMID: 18989472)
Org Lett. 2005 Nov 24;7(24):5401-4. (PMID: 16288516)
Org Lett. 2015 Mar 20;17(6):1461-4. (PMID: 25730626)
Angew Chem Int Ed Engl. 2014 Aug 18;53(34):9068-71. (PMID: 24975733)
J Chem Phys. 2008 Feb 28;128(8):084106. (PMID: 18315032)
Angew Chem Int Ed Engl. 2015 Oct 12;54(42):12236-73. (PMID: 26436516)
Inorg Chem. 2003 May 19;42(10):3293-307. (PMID: 12739971)
Angew Chem Int Ed Engl. 2011 Jun 6;50(24):5564-7. (PMID: 21567696)
Chem Commun (Camb). 2009 Sep 7;(33):4929-37. (PMID: 19668807)
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Contributed Indexing:
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Keywords: N,P ligands; cooperative effects; coordination modes; homogeneous catalysis; ligand design
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Substance Nomenclature:
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0 (Ligands)
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Entry Date(s):
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Date Created: 20210817 Date Completed: 20211008 Latest Revision: 20240403
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Update Code:
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20240403
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PubMed Central ID:
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PMC8519111
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DOI:
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10.1002/chem.202101921
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PMID:
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34403555
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Novel seven-membered cyclic imine-based 1,3-P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These "cycloiminophosphanes" possess flexible non-isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P-κ 1 - and P,N-κ 2 -tungsten(0) carbonyl complexes, by determining the IR frequency of the trans-CO ligands. Complexes with [RhCp*Cl 2 ] 2 demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ 1 and κ 2 species; treatment with AgOTf gives full conversion to the κ 2 complex. The potential for catalysis was shown in the Ru II -catalyzed, solvent-free hydration of benzonitrile and the Ru II - and Ir I -catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l-menthone, as well as their P,N-κ 2 -Rh III and a P-κ 1 -Ru II complexes.
(© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
