Abstract
Complexes [(C4Me4)Co(CO)(2){Co(P(2)C(2)tBu(2))(2)}] (1, C4Me4 = tetramethylcyclobutadiene) and [CpNi{Co(P(2)C(2)tBu(2))(2)}-(PPh3)] (2, Cp = cyclopentadienyl) were synthesized by transmetalating [Tl(thf)(2){Co(P(2)C(2)tBu(2))(2)}] with [(C4Me4)Co(CO)(2)I] and [CpNiBr(PPh3)]. Compounds 1 and 2 were fully characterized by X-ray crystallography, multinuclear NMR, UV/Vis, and IR spectroscopy, and ...
Abstract
Complexes [(C4Me4)Co(CO)(2){Co(P(2)C(2)tBu(2))(2)}] (1, C4Me4 = tetramethylcyclobutadiene) and [CpNi{Co(P(2)C(2)tBu(2))(2)}-(PPh3)] (2, Cp = cyclopentadienyl) were synthesized by transmetalating [Tl(thf)(2){Co(P(2)C(2)tBu(2))(2)}] with [(C4Me4)Co(CO)(2)I] and [CpNiBr(PPh3)]. Compounds 1 and 2 were fully characterized by X-ray crystallography, multinuclear NMR, UV/Vis, and IR spectroscopy, and elemental analysis. Their molecular structures show s-coordination of one phosphorus atom of the [Co(P(2)C(2)tBu(2))(2)]anion to the second metal atom (cobalt or nickel). Time-dependent density functional theory (TD-DFT) calculations were applied to gain insight into the electronic structures and the nature of the electronic transitions observed in the UV/Vis spectra. Cyclic voltammetry studies revealed the similar redox behavior of 1 and 2, which are reversibly oxidized to the corresponding monocations 1(+) and 2(+) with retention of the di-nuclear structures. The cyclic voltammograms furthermore show that 1 and 2 decompose upon reduction with cleavage of the dinuclear structures into the free [Co(P(2)C(2)tBu(2))(2)](-) anion and further uncharacterized products.
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