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|標題:||Further investigations of linear trirhodium complexes: experimental and theoretical studies of Rh-3(dpa)(4)Cl-2 and Rh-3(dpa)(4)Cl-2 (BF4) dpa = bis(2-pyridyl)amido anion||作者:||Huang, G.C.
|關鍵字:||metal string complexes;bond-stretch isomerism;2-step spin-crossover;crystal-structure;transition-metal;tripyridyldiamido dianion;electronic-properties;magnetic-properties;approximation;oxidation||Project:||Dalton Transactions||期刊/報告no：:||Dalton Transactions, Issue 14, Page(s) 2623-2629.||摘要:||
The linear trirhodium compound, Rh-3(dpa)(4)Cl-2 (1), and its one-electron oxidation product, [Rh-3(dpa)(4)Cl-2]BF4 (2), have been synthesized and studied extensively. The magnetic measurement for compound 1 shows that it possesses one unpaired electron that is assigned to occupy the sigma(nb) orbital ((2)A(2)) by DFT calculations. Upon oxidation, a beta-spin electron of 1 is removed, that causes compound 2 to exhibit a triplet ground state. DFT calculations indicate that the two unpaired electrons of 2 occupy sigma(nb) and delta* orbitals (B-3(1)), which is supported by H-1 NMR spectrum. Unlike their isoelectronic analogues [Co-3(dpa)(4)Cl-2] (3) and [Co-3(dpa)(4)(Cl)(2)]BF4 (4), both compound 1 and 2 do not display the spin-crossover phenomenon. The reason may be attributed to the relative large energy gap between B-3(1) and open-shell singlet B-1(1) states.
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