Synthesis and Characterization of Heterobimetallic (Pd/B) Nindigo Complexes and Comparisons to Their Homobimetallic (Pd2, B2) Analogues
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- 作者：Graeme Nawn ; Robert McDonald ; Robin G. Hicks
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：October 7, 2013
- 年：2013
- 卷：52
- 期：19
- 页码：10912-10919
- 全文大小：407K
- 年卷期：v.52,no.19(October 7, 2013)
- ISSN：1520-510X
文摘
Reactions of Nindigo-BF2 complexes with Pd(hfac)2 produced mixed complexes with Nindigo binding to both a BF2 and a Pd(hfac) unit. These complexes are the first in which the Nindigo ligand binds two different substrates, and provide a conceptual link between previously reported bis(BF2) and bis(Pd(hfac)) complexes. The new Pd/B complexes have intense near IR absorption near 820 nm, and they undergo multiple reversible oxidations and reductions as probed by cyclic voltammetry experiments. The spectral, redox, and structural properties of these complexes are compared against those of the corresponding B2 and Pd2 complexes with the aid of time-dependent density functional calculations. In all cases the low-energy electronic transitions are ligand-centered 蟺鈥撓€* transitions, but the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies鈥攁nd hence the absorption wavelength as well as the oxidation and reduction potentials鈥攁re significantly modulated by the moieties bound to the Nindigo ligand.