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Article

Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence

1
Department of Chemistry and Science, Materials Sciences Center, Philipps University of Marburg, 35043 Marburg, Germany
2
Institute for Physical Chemistry, University of Regensburg, 93040 Regensburg, Germany
*
Author to whom correspondence should be addressed.
Academic Editor: Yves Canac
Molecules 2020, 25(17), 3990; https://doi.org/10.3390/molecules25173990
Received: 20 July 2020 / Revised: 27 August 2020 / Accepted: 29 August 2020 / Published: 1 September 2020
(This article belongs to the Special Issue Carbon Ligands: From Fundamental Aspects to Applications)
A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single-crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone pairs involved in the binding of two geminal L-Cu(I) fragments at Cu–Cu distances in the range 2.55–2.67 Å. In order to enhance conformational rigidity within the characteristic Cu–C–Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2–9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 1418. Neutral complexes were typically obtained via the reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via the salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalents of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of bisphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), or 1,1′-bis(diphenyl-phosphino) ferrocene (dppf). For the first time, carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared, and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (ΦPL) were determined to be 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16). View Full-Text
Keywords: carbodiphosphorane; phosphorus ylides; pincer ligands; coordination chemistry; Cu(I) complex; photoluminescence carbodiphosphorane; phosphorus ylides; pincer ligands; coordination chemistry; Cu(I) complex; photoluminescence
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MDPI and ACS Style

Klein, M.; Demirel, N.; Schinabeck, A.; Yersin, H.; Sundermeyer, J. Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence. Molecules 2020, 25, 3990. https://doi.org/10.3390/molecules25173990

AMA Style

Klein M, Demirel N, Schinabeck A, Yersin H, Sundermeyer J. Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence. Molecules. 2020; 25(17):3990. https://doi.org/10.3390/molecules25173990

Chicago/Turabian Style

Klein, Marius, Nemrud Demirel, Alexander Schinabeck, Hartmut Yersin, and Jörg Sundermeyer. 2020. "Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence" Molecules 25, no. 17: 3990. https://doi.org/10.3390/molecules25173990

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