P. Paul et K. Venkatasubramanian, REACTIONS OF A DINUCLEAR COPPER(I) COMPLEX DERIVED FROM A HEXADENTATELIGAND HAVING N2AS4 DONOR SITES - CRYSTAL-STRUCTURE OF [CU2(BDAE)(PPH3)2CL2], Polyhedron, 12(7), 1993, pp. 835-845
The reactions of a tri-coordinate dinuclear copper(I) complex of the c
omposition [Cu2(BDAE)](ClO4)2 (Where BDAE = pha'-bis{bis[2-(diphenylar
sino)ethyl]amino}ethane) with some mono- and bidentate species having
different donor atoms were studied. The reaction of the complex with a
nionic species such as LiCl, NaN3, NH4NCS and NaBH4 resulted in the fo
rmation of tetra-coordinate complexes of compositions [Cu2(BDAE)Cl2],
[Cu2(BDAE)(N3)](ClO4), [Cu2(BDAE)(NCS)](ClO4) and [Cu2(BDAE)(BH4)2], r
espectively. The reactions of CS2 and thiourea gave the products [Cu2(
BDAE)(CS2)2](ClO4)2 and [Cu2(BDAE)(H2NCSNH2)2](ClO2)2, respectively. T
he reactions of monodentate neutral molecules B (B = PPh3, AsPh3 and i
midazole) yielded complexes of the composition [Cu2(BDAE)(B)2](ClO4)2.
The reaction with pyridine in a 1:4 molar ratio gave a complex of com
position [Cu2(BDAE)(C5H5N)4](ClO4)2. The bidentate ligands 1,2-bis(dip
henylphosphino)methane/ethane (dppm/dppe) react with the complex to yi
eld complexes of the composition [Cu2(BDAE)(dppm)](ClO4)2/[Cu2(BDAE)(d
ppe)](ClO4)2, in which dppm/dppe acts as a bridge between two metal ce
ntres. The reaction with bipyridine gave a tetra-coordinate complex of
the composition [Cu2(BDAE)(C10H8N2)2](ClO4)2. The molecular structure
of the complex [Cu2(BDAE)(PPh3)2Cl2] was established by single-crysta
l X-ray diffraction. The cyclic voltammetric behaviour of all of these
complexes was investigated.