Synthesis, characterization, structures and reactivities of dinuclear copper(I) complexes of three new binucleating hexadentate ligands having N2P4 or N2As4 donor sites
Abstract
Three new binucleating hexadentate ligands having N2P4 or N2As4 donor sites, viz. N,N,N′,N′-tetrakis-[2-(diphenylphosphino)ethyl] ethane-1,2-diamine (L1), its arsine analogue (L2) and 1,3-bis{bis[2-(diphenylphosphino)ethyl]aminomethyl}benzene (L3) have been prepared. The ligands react with [Cu(PPh3)3Cl] to give the dinuclear four-co-ordinate copper(I) complexes [Cu2(L1)(PPh3)2Cl2], [Cu2(L2)(PPh3)2Cl2] and [Cu2(L3)Cl2]. With [Cu(NCMe)4][ClO4] the ligands yielded the three-co-ordinate dinuclear complexes [Cu2L][ClO4]2(L = L1, L2 or L3), which on treatment with NaN3. NH4NCS, KOH or NaBH4(L = L1 or L3) gave dinuclear four-co-ordinate copper(I) complexes [Cu2L(X)2](X = N3, NCS, OH or BH4)via elimination of perchlorate and co-ordination of X. For the tetrahydroborato complexes, two hydrogen atoms of each BH4– ligand were co-ordinated to separate copper(I) centres. All the new ligands and complexes were characterized on the basis of elemental analysis, molar conductivity, IR spectra and 1H, 13C-{1H}, 11B-{1H} and 31P-{1H} NMR spectral data. The molecular structures of [Cu2(L1)(PPh3)2Cl2]1 and [Cu2(L3)Cl2]3 were established by single-crystal X-ray diffraction [crystal data: 1, C94H90Cl2Cu2N2P6, triclinic, space group P, a= 11.711(2), b= 18.731(3), c= 10.080(1)Å, α= 91.22(1), β= 107.45(1), γ= 78.11(1)°, Z= 1, final R factor 0.040 (R′= 0.046) for 3715 observed reflections; 3, C64H64Cl2Cu2N2P4, triclinic, space group P
, a= 12.922(4), b= 19.161(1), c= 12.777(3), Å, α= 93.11(1), β= 111.85(2), γ= 84.69(1)°, Z= 2, final R factor 0.042 (R′= 0.046) for 5684 observed reflections].