Structural Diversity and Rare η1 Cu-C Interactions in CuI Complexes of 1,2,3-Triazole-Functionalized Bisphosphines.

This manuscript describes the synthesis of copper complexes of 1,2,3-triazolyl-phosphines: o-Ph2P(C6H4){1,2,3-N3CC6H5)C(PPh2)} (L1), (C6H5){1,2,3-N3C(C6H4(o-PPh2))-C(PPh2)} (L2), 3-Ph2P(C5H3N){1,2,3-N3C(C6H5)C(PPh2)} (L3), o-Ph2P(C6H4){1,2,3-N3C(C5H5N)C(PPh2)} (L4), and {(3,5-Ph2PC6H4-o)21,2,3-N3CCH} (L5). The reactions of L1-L3 with CuI salts afforded dimeric complexes having the general formula [Cu2(μ -X)2L2] (L = L1, X = Cl, Br and I: 1 - 3; L= L2, X = Cl, Br and I: 4- 6; L = L3; X = Cl, Br, and I: 7-9). The reaction of L4 with CuI in a 1:2 molar ratio afforded 1D-coordination polymer [{(CuI)2{o-Ph2P(C6H4){1,2,3-N3C(C5H5N)C(PPh2)}-μ-((k1-N)(k2-P,P))}}]n (10). The reaction of L5 with cuprous halides (CuX) (X = Br, I) yielded mononuclear complexes [CuX{(3,5-Ph2PC6H4-o)21,2,3-N3CCH}-κ2P,P] (X = Br, 12; I, 13). Crystal structures of complexes 12 and 13 showed close interactions between CuI and the triazole C7 carbon. These relatively short Cu···C7 separations may be due to the η1-C interaction (dπ-pπ bond) between the triazolic carbon atom (via pz orbital) and CuI or three-centered two-electron interaction between CuI and the triazolic C-H bond. The existence of the Cu···C interaction was further evinced by the QTAIM analysis in compounds 12 and 13.