Structural and spectroscopic characterization of five coordinate iron and cobalt bis(dithiolene)-trimethylphosphine complexes
| Autor: | P. Chandrasekaran, Troy Selby-Karney, Eyglo Wright, David A. Grossie, Kuppuswamy Arumugam |
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| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Organic Chemistry Trimethylphosphine chemistry.chemical_element Infrared spectroscopy 010402 general chemistry Photochemistry 01 natural sciences Square pyramidal molecular geometry 0104 chemical sciences Analytical Chemistry Inorganic Chemistry Metal chemistry.chemical_compound Crystallography chemistry Intramolecular force visual_art visual_art.visual_art_medium Homoleptic Cobalt Spectroscopy Phosphine |
| Zdroj: | Journal of Molecular Structure. 1141:477-483 |
| ISSN: | 0022-2860 |
| Popis: | Heteroleptic bis(dithiolene)-phosphine iron and cobalt complexes [Fe(adt)2(PMe3)] (1) and [Co(adt)2(PMe3)] (2) (adt = para-anisyldithiolene) have been synthesized from corresponding bis(dithiolene) dimers [M2(adt)4]2 (M = Fe, Co) by reacting with excess PMe3 in dichloromethane. Solid-state structures of 1 and 2 have been determined by single crystal X-ray crystallography, and the dithiolene ligands C S (≈1.72 A) and C C (≈1.37 A) bond distances reveal the coordination of π-radical monoanionic dithiolene (adt•1−) ligands to metal centers. Intense low energy ligand-to-ligand-charge transfer (LLCT) absorption band (743 nm for 1; 905 nm for 2) in UV–vis spectra and characteristic ν(C S•) (1168 cm−1 for 1; 1170 cm−1 for 2) in IR spectra affirms coordination of π-radical monoanionic dithiolenes to divalent metal ions. The cyclic voltammogram of 1 and 2 shows reversible oxidation and reduction waves attributed to MII → MIII + e− (+0.52 V for 1; +0.29 V for 2) and adt•1− + e− → adt2− (−0.63 V for 1; −0.46 V for 2) redox process respectively. Comprehensive structural and spectroscopic investigations conclude, [M2III(adt2−)2(adt•1-)2] → 2 [MII(adt•1-)2(PMe3)] intramolecular redox interplay during phosphine coordination induced cleavage of homoleptic bis(dithiolene) dimers to produce square pyramidal complexes. |
| Databáze: | OpenAIRE |
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