Steric and hydrogen-bonding effects on the stability of copper complexes with small molecules

Inorganic Chemistry
Akira WadaHideki Masuda

Abstract

A series of the copper(II) complexes with tripodal tetradentate tris(pyridyl 2-methyl)amine-based ligands possessing the hydrogen-bonding 6-aminopyridine units (tapa, three amino groups; bapa, two amino groups; mapa, one amino group) have been synthesized, and their copper(II) complexes with a small molecule such as dioxygen and azide have been studied spectroscopically and structurally. The reaction of their Cu(II) complexes with NaN(3) have given the mononuclear copper complexes with azide in an end-on mode, [Cu(tapa)(N(3))]ClO(4) (1a), [Cu(bapa)(N(3))]ClO(4) (2a), [Cu(mapa)(N(3))]ClO(4) (3a), and [Cu(tpa)(N(3))]ClO(4) (4a) (tpa, no amino group). The crystal structures have revealed that the coordination geometries around the metal centers are almost a trigonal-bipyramidal rather than a square-planar except for 1a with an intermediate between them. The UV-vis and ESR spectral data indicate that the increase of NH(2) groups of ligands causes the structural change from trigonal-bipyramidal to square-pyramidal geometry, which is regulated by a combination of steric repulsion and hydrogen bond. The steric repulsion of amino groups with the azide nitrogen gives rise to elongation of the Cu-N(py) bonds, which leads to the positive ...Continue Reading

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Citations

Mar 29, 2012·Inorganic Chemistry·Christopher S LetkoDanielle L Gray
Dec 19, 2012·Inorganic Chemistry·Matthew A ThorsethAndrew A Gewirth
Sep 12, 2008·Inorganic Chemistry·Debabrata MaitiKenneth D Karlin
Dec 17, 2008·Chemical Communications : Chem Comm·Ryan L Shook, A S Borovik
May 8, 2010·Chemical Communications : Chem Comm·Young Jun ParkA S Borovik
Feb 16, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Nathaniel S SickermanA S Borovik
Apr 13, 2018·Chemical Communications : Chem Comm·Samuel I MannA S Borovik
Nov 15, 2016·European Journal of Inorganic Chemistry·Benjamin D NeisenWilliam B Tolman
May 12, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Juan C Mareque RivasSimon Parsons
Jul 25, 2019·Angewandte Chemie·Michiel Langerman, Dennis G H Hetterscheid
Apr 11, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Tatsuya FujiiHideki Masuda
Oct 18, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ellen M MatsonAlison R Fout
Dec 16, 2017·Chemical Communications : Chem Comm·E W DahlN K Szymczak
Mar 1, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Fawaz A SaadBenson M Kariuki
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Jun 30, 2018·Journal of the American Chemical Society·Mayukh BhadraKenneth D Karlin
Mar 25, 2014·Inorganic Chemistry·Cameron M MooreNathaniel K Szymczak
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May 4, 2007·Journal of the American Chemical Society·Debabrata MaitiKenneth D Karlin
Aug 15, 2006·Inorganic Chemistry·Laurent MetteauJuan C Mareque-Rivas

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