FULL PAPER DOI: 10.1002/ejic.201000165 Synthesis, Characterisation and Luminescent Properties of Mixed-Ligand Copper(I) Complexes Incorporating N-Thiophosphorylated Thioureas and Phosphane Ligands Maria G. Babashkina, [a] Damir A. Safin,* [a] Axel Klein,* [a] and Michael Bolte [b] Keywords: Chelate complexes / Copper / Crystal Structure / Luminescence / Phosphanes / Thiourea The potassium salts of H 2 NC(S)NHP(S)(OiPr) 2 (HL I ) or o- C 6 H 4 [NHC(S)NHP(S)(OiPr) 2 ] 2 (H 2 L II ) react with [Cu(PPh 3 ) 3 I] or a mixture of CuI and Ph 2 P(CH 2 ) 1–3 PPh 2 or Ph 2 P(C 5 H 4 - FeC 5 H 4 )PPh 2 in aqueous EtOH/CH 2 Cl 2 to give mononuclear complexes [Cu(PPh 3 )L I ] (1), [Cu{Ph 2 P(CH 2 ) 2 PPh 2 }L I ] (2), [Cu{Ph 2 P(CH 2 ) 3 PPh 2 }L I ](3) or [Cu{Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 }- L I ](4), or dinuclear complexes [Cu 2 (Ph 2 PCH 2 PPh 2 )L I 2 ](5), [Cu 2 (PPh 3 ) 2 L II ](6), [Cu 2 {Ph 2 P(CH 2 ) 2 PPh 2 } 2 L II ](7), [Cu 2 {Ph 2 P- Introduction In preceding papers we described heteroligand complexes of Cu I with a number of N-thiophosphorylated thioureas and thioamide RC(S)NHP(S)(OiPr) 2 [R = morpholin-4-yl, piperidin-1-yl, [1] (1-naphthyl)NH, [2] NH 2 (HL I ), [1,3] (pyr- idin-2-yl)NH, (pyridin-3-yl)NH, H 2 N-6-Py-2-NH, [4] Ph, Et 2 N, [5–7] (EtO) 2 P(O)CH 2 C 6 H 4 -4-NH, [8] MeNH, iPrNH, tBuNH, Me 2 N, PhNH, 2,6-Me 2 C 6 H 3 NH, 2,4,6- Me 3 C 6 H 2 NH [9–11] ] and triphenylphosphane or Ph 2 P- (CH 2 ) 1–3 PPh 2 and Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 . We also showed that the reactions of alkaline salts of the tetrakis- Scheme 1. [a] Institut für Anorganische Chemie, Universität zu Köln, Greinstrasse 6, 50939 Köln, Germany Fax: +49-221-4705196 E-mail: damir.safin@ksu.ru axel.klein@uni-koeln.de [b] Institut für Anorganische Chemie, J.-W.-Goethe-Universität, 60438 Frankfurt/Main, Germany Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/ejic.201000165. View this journal online at wileyonlinelibrary.com © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Inorg. Chem. 2010, 4018–4026 4018 (CH 2 ) 3 PPh 2 } 2 L II ](8), [Cu 2 {Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 } 2 L II ](9) or [Cu 2 (Ph 2 PCH 2 PPh 2 )L II ](10). The structures of these com- pounds were investigated by 1 H and 31 P{ 1 H} NMR, UV/Vis spectroscopy and elemental analysis. The crystal structures of H 2 L II , 1, 3–6, 8 and 10 were determined by single-crystal X-ray diffraction. The luminescent properties of complexes 1–10 in the solid state are reported. thiourea containing a cyclam fragment with [Cu(PPh 3 ) 3 I] lead to the tetranuclear Cu I complex [{Cu(PPh 3 ) 2 } 4 - (cyclam)] (Scheme 1). [12] We have also described a number of N-(thio)phosphoryl- ated bis(thio)ureas, which are potentially bridging ligands, and investigated their complexation properties towards various metal cations. [6,13–20] Only one dinuclear hetero- ligand complex of Cu I with N-thiophosphoryl bis(thio- urea), containing 1,10-diaza-18-crown-6, and PPh 3 (Scheme 1) has been described. [6] To the best of our knowl- edge there are no crystal structures of such types of com- plexes. Furthermore, we have described two Cu I complexes [CuPPh 3 {RC(S)NP(S)(OiPr) 2 }] (R = H 2 N-6-Py-2-NH, [4] (EtO) 2 P(O)CH 2 C 6 H 4 -4-NH [8] ) containing one triphen- ylphosphane (PPh 3 ) ligand. A number of heteroligand Cu I complexes containing both aryl-substituted pnictides and cyclic thioureas or pyridinethiolates have also been de- scribed. [21–23] A combination of these two types of ligands might lead to interesting and unusual photophysical and electrochemical properties. [24]