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Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6]

Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland
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Inorganics 2019, 7(1), 11; https://doi.org/10.3390/inorganics7010011
Received: 17 December 2018 / Revised: 11 January 2019 / Accepted: 15 January 2019 / Published: 18 January 2019
(This article belongs to the Special Issue Novel Ligand Design in Coordination Compounds)
We report the synthesis and characterization of [Cu(P^P)(N^S)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl) ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) and N^S = 2-(iso-propylthio)pyridine (iPrSpy) or 2-(tert-butylthio)pyridine (tBuSpy). The single crystal structures of [Cu(POP)(iPrSPy)][PF6] and [Cu(POP)(tBuSPy)][PF6] have been determined and confirm a distorted tetrahedral copper(I) centre and chelating P^P and N^S ligands in each complex. Variable temperature (VT) 1H and 31P{1H} NMR spectroscopy reveals dynamic behavior with motion of the POP backbone in [Cu(POP)(iPrSPy)][PF6] and [Cu(POP)(tBuSPy)][PF6] frozen out at 238 K. VT NMR spectroscopic data including EXSY peaks in the ROESY spectrum of [Cu(xantphos)(tBuSPy)][PF6] at 198 K reveal that two conformers exist in an approximate ratio of 5:1. Replacing bpy by the N^S ligands shifts the Cu+/Cu2+ oxidation to a higher potential. The copper(I) compounds are weak emitters in the solid state with PLQY values of <2%. These values are similar to those for [Cu(POP)(bpy)][PF6] and [Cu(xantphos)(bpy)][PF6] in the solid state. View Full-Text
Keywords: Copper; coordination complex; 2-(alkylthio)pyridine; bis(phosphane); X-ray structure; dynamic behavior Copper; coordination complex; 2-(alkylthio)pyridine; bis(phosphane); X-ray structure; dynamic behavior
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Nohara, I.; Prescimone, A.; Housecroft, C.E.; Constable, E.C. Softening the Donor-Set: From [Cu(P^P)(N^N)][PF6] to [Cu(P^P)(N^S)][PF6]. Inorganics 2019, 7, 11.

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