Metal-metal interactions in tetrakis(diphenylphosphino)benzene-bridged dimetallic complexes and their related coordination polymers
- Univ. of Texas, Austin, TX (United States)
Electrochemical, EPR, and spectroelectrochemical methods have been used to probe electronic coupling through a 1,2,4,5-tetrakis(diphenylphosphino)benzene bridging ligand connecting metal centers in several Ni-, Pd-, and Pt-containing dimetallic complexes. These dimetalated complexes showed weak intervalence charge transfer (IT) bands and slightly shifted redox potentials in comparison with their monometallic models. A Marcus-Hush analysis of the energies of the IT bands for the electrochemically generated mixed-valence heterodimetallic complexes (Ni{sup o}-Pd{sup II} and Ni{sup o}-Pt{sup II}, respectively) established the magnitude of intermetallic electronic coupling. The weak thermal coupling observed in these dimetalated complexes is consistent with the very low conductivities (10{sup {minus}8}-10{sup {minus}10}{omega}{sup -1} cm{sup {minus}1}) observed in the polymeric analogs of these complexes, namely, the newly prepared metal coordination polymers (M = Ni{sup II}, Pd{sup II}, Pt{sup II}) with 1,2,4,5-tetrakis(diphenylphosphino)benzene.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 420938
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 13; Other Information: PBD: 22 Jun 1994
- Country of Publication:
- United States
- Language:
- English
Similar Records
Investigation of the photochemical, electrochemical, and spectroelectrochemical properties of an iridium(III)/ruthenium(II) mixed-metal complex bridged by 2,3,5,6-tetrakis(2-pyridyl)pyrazine
Heterodifunctional ligands derived from monooxidized Bis(phosphino)amines. Synthesis and transition metal (Molybdenum(0), Tungsten(0), Rhodium(I), Palladium(II), and Platinum(II)) complexes of (Diphenylphosphino)(diphenylphosphinothioyl)- and (Diphenylphosphino) (diphenylphosphinoselenoyl)phenylamine, Ph[sub 2]PN(Ph)P(E)PH[sub 2] (E = S, Se). Crystal and molecular structure of the Pt(II) Complex [Cl[sub 2]P[ovr tPPh[sub 2]N(Ph)P(S)]Ph[sub 2]][center dot]H[sub 2]O