Synthesis, Characterization, Structures and Reactivities of Dinuclear Copper(I) Complexes of Three New Binucleating Hexadentate Ligands Having N2P4 or N2As4 Donor Sites

DOI: 10.1039/DT9910003405

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Journal of the Chemical Society, Dalton Transactions p. 3405 - 3412 (1991)

Update date:2022-09-26

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Authors:

Khan, Mirza Mohammed Taqui

Paul, Parimal

Venkatasubramanian, Krishnan

Purohit, Sapna

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Article abstract of DOI:10.1039/DT9910003405

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 to give the dinuclear four-co-ordinate copper(I) complexes 1)(PPh3)2Cl2>, 2)(PPh3)2Cl2> and 3)Cl2>.With the ligands yielded the three-co-ordinate dinuclear complexes 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 (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) centers.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 1)(PPh3)2Cl2> 1 and 3)Cl2> 3 were established by single-crystal X-ray diffraction , a = 11.711(2), b = 18.731(3), c = 10.080(1) Angstroem, α = 91.22(1), β = 107.45(1), γ = 78.11(1) deg, Z = 1, final R factor 0.040 (R'= 0.046) for 3715 observed reflections; 3, C64H64Cl2Cu2N2P4, triclinic, space group P1<*>, a = 12.922(4), b = 19.161(1), c = 12.777(3) Angstroem, α = 93.11(1), β = 111.85(2), γ = 84.69(1) deg, Z = 2, final R factor 0.042 (R'= 0.046) for 5684 observed reflections>.

Full text of DOI:10.1039/DT9910003405

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