The Coordination Behavior of Oxygen-depleted Calixarenes towards d10 Noble Metal Ions

Matthias Keck; Santina Hoof; Varun Rawat; Arkadi Vigalok; Christian Limberg

doi:10.1002/zaac.202000138

The Coordination Behavior of Oxygen-depleted Calixarenes towards d¹⁰ Noble Metal Ions

Matthias Keck, Santina Hoof, Varun Rawat, Arkadi Vigalok, Christian Limberg^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

A calix[4]arene, in which two of the phenol functions are replaced by pyrazole units, [H₂(bpzCal)], was investigated as a ligand for Cu⁺, Ag⁺ and Au⁺ ions. Using [Cu(MeCN)₄]BF₄ and AgSbF₆ as the precursors, complexes [MH₂(bpzCal)]X (M = Cu, X = BF_4; M = Ag, X = SbF₆) were formed, where the calixarene ligands adopt a 1,3-alternate structure and the metal ions are coordinated linearly by the two pyrazolyl donors. [CuH₂(bpzCal)]BF₄ displayed a – for copper(I) complexes – unusual stability towards O₂, which is due to the steric protection of the Cu^I center. By contrast a dinuclear copper(I) complex [Cu₂(bpzCal)] that was obtained through treatment of [H₂(bpzCal)] with two equivalents of Cu(HMDS) is rather sensitive towards O₂. The preparation of a gold complex required the employment of a gold precursor, which contains one labile and one stabilizing neutral ligand, namely [(PPh₃)Au(NCMe)]SbF₆, which led to the formation of [(PPh₃)AuH₂(bpzCal)]SbF₆. In this complex [H₂(bpzCal)] acts only as a monodentate ligand for the gold center. Taken together, the results demonstrate the potential of [H₂(bpzCal)] in providing rather different coordination spheres for metal ions.

Original language	English
Pages (from-to)	904-908
Number of pages	5
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	646
Issue number	13
DOIs	https://doi.org/10.1002/zaac.202000138
State	Published - 15 Jul 2020

Funding

Funders	Funder number
G.I.F.
German Israeli Foundation for Scientific Research and Development
German-Israeli Foundation for Scientific Research and Development
Humboldt-Universität zu Berlin

Keywords

Calixarenes
Coordination modes
Copper
Gold
Silver

Access to Document

10.1002/zaac.202000138

Cite this

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title = "The Coordination Behavior of Oxygen-depleted Calixarenes towards d10 Noble Metal Ions",

abstract = "A calix[4]arene, in which two of the phenol functions are replaced by pyrazole units, [H2(bpzCal)], was investigated as a ligand for Cu+, Ag+ and Au+ ions. Using [Cu(MeCN)4]BF4 and AgSbF6 as the precursors, complexes [MH2(bpzCal)]X (M = Cu, X = BF4; M = Ag, X = SbF6) were formed, where the calixarene ligands adopt a 1,3-alternate structure and the metal ions are coordinated linearly by the two pyrazolyl donors. [CuH2(bpzCal)]BF4 displayed a – for copper(I) complexes – unusual stability towards O2, which is due to the steric protection of the CuI center. By contrast a dinuclear copper(I) complex [Cu2(bpzCal)] that was obtained through treatment of [H2(bpzCal)] with two equivalents of Cu(HMDS) is rather sensitive towards O2. The preparation of a gold complex required the employment of a gold precursor, which contains one labile and one stabilizing neutral ligand, namely [(PPh3)Au(NCMe)]SbF6, which led to the formation of [(PPh3)AuH2(bpzCal)]SbF6. In this complex [H2(bpzCal)] acts only as a monodentate ligand for the gold center. Taken together, the results demonstrate the potential of [H2(bpzCal)] in providing rather different coordination spheres for metal ions.",

keywords = "Calixarenes, Coordination modes, Copper, Gold, Silver",

author = "Matthias Keck and Santina Hoof and Varun Rawat and Arkadi Vigalok and Christian Limberg",

note = "Publisher Copyright: {\textcopyright} 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.",

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T1 - The Coordination Behavior of Oxygen-depleted Calixarenes towards d10 Noble Metal Ions

AU - Keck, Matthias

AU - Hoof, Santina

AU - Rawat, Varun

AU - Vigalok, Arkadi

AU - Limberg, Christian

PY - 2020/7/15

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N2 - A calix[4]arene, in which two of the phenol functions are replaced by pyrazole units, [H2(bpzCal)], was investigated as a ligand for Cu+, Ag+ and Au+ ions. Using [Cu(MeCN)4]BF4 and AgSbF6 as the precursors, complexes [MH2(bpzCal)]X (M = Cu, X = BF4; M = Ag, X = SbF6) were formed, where the calixarene ligands adopt a 1,3-alternate structure and the metal ions are coordinated linearly by the two pyrazolyl donors. [CuH2(bpzCal)]BF4 displayed a – for copper(I) complexes – unusual stability towards O2, which is due to the steric protection of the CuI center. By contrast a dinuclear copper(I) complex [Cu2(bpzCal)] that was obtained through treatment of [H2(bpzCal)] with two equivalents of Cu(HMDS) is rather sensitive towards O2. The preparation of a gold complex required the employment of a gold precursor, which contains one labile and one stabilizing neutral ligand, namely [(PPh3)Au(NCMe)]SbF6, which led to the formation of [(PPh3)AuH2(bpzCal)]SbF6. In this complex [H2(bpzCal)] acts only as a monodentate ligand for the gold center. Taken together, the results demonstrate the potential of [H2(bpzCal)] in providing rather different coordination spheres for metal ions.

AB - A calix[4]arene, in which two of the phenol functions are replaced by pyrazole units, [H2(bpzCal)], was investigated as a ligand for Cu+, Ag+ and Au+ ions. Using [Cu(MeCN)4]BF4 and AgSbF6 as the precursors, complexes [MH2(bpzCal)]X (M = Cu, X = BF4; M = Ag, X = SbF6) were formed, where the calixarene ligands adopt a 1,3-alternate structure and the metal ions are coordinated linearly by the two pyrazolyl donors. [CuH2(bpzCal)]BF4 displayed a – for copper(I) complexes – unusual stability towards O2, which is due to the steric protection of the CuI center. By contrast a dinuclear copper(I) complex [Cu2(bpzCal)] that was obtained through treatment of [H2(bpzCal)] with two equivalents of Cu(HMDS) is rather sensitive towards O2. The preparation of a gold complex required the employment of a gold precursor, which contains one labile and one stabilizing neutral ligand, namely [(PPh3)Au(NCMe)]SbF6, which led to the formation of [(PPh3)AuH2(bpzCal)]SbF6. In this complex [H2(bpzCal)] acts only as a monodentate ligand for the gold center. Taken together, the results demonstrate the potential of [H2(bpzCal)] in providing rather different coordination spheres for metal ions.

KW - Calixarenes

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