201409-90-7Relevant academic research and scientific papers
Synthesis and reactions of coordinatively unsaturated 16-electron chalcogenolate complexes, Ru(EAr) 2(η6-arene) and cationic binuclear chalcogenolate complexes, [(η6-arene) Ru(μ-EPh) 3Ru( η6-arene) ]PF6
Mashima, Kazushi,Kaneko, Sei-Ichi,Tani, Kazuhide,Kaneyoshi, Hiromu,Nakamura, Akira
, p. 345 - 356 (2007/10/03)
Coordinatively unsaturated 16-electron ruthenium-selenolate complexes (η6-arene)Ru(Se-2,4,6-C6H2Me3)2 [arene = p-CH3C6H4(CHMe2) (5b), C6Me6 (5c)] have been prepared by treating [((η6-arene)RuCl2]2 (1) with sodium salt of 2,4,6-trimethylphenyl-selenolate in methanol. The complexes 5 are compared with the thiolate complexes such as (η6-arene)Ru(SAr)2 [SAr = 2,6-dimethylbenzenethiolate (2), SAr = 2,4,6-tri(isopropyl)benzenethiolate (3), (SAr)2 = 1,2-benzenedithiolate (4); arene = C6H6 (a), p-CH3C6H4(CHMe2) (b), C6Me6 (c)], which have been recently prepared by us. However, the tellurolate analog has not been obtained in similar manner. These selenolate complexes are dark green, being ascribed to the LMCT band [pπ(Se) → dπ * (Ru)]. The absorption bands of 5 are red-shifted compared to the thiolate complexes. In contrast to the bulky substituted chalcogenolate ligand system, the reaction of 1 with PhENa followed by the addition of KPF6 resulted in the formation of the cationic binuclear chalcogenolate complexes [(ηη6-arene)Ru(μ-E-Ph)3Ru(η6-arene)](PF6) [E = Se (7), E = Te (8); arene = p-CH3C6H4(CHMe2) (b), C6Me6 (c)]. Reactions of the 16-electron thiolate and selenolate complexes with σ-donor molecules such as DMSO, hydrazine and ammonia along with some electrophiles were investigated. DMSO can coordinate with the thiolate complex 2a to give a DMSO adduct of 9, which was characterized spectroscopically and crystallographically. The strength of complexation of hydrazine and ammonia to the thiolate and selenolate complexes 2, 3, 4c and 5 depends on the effective electron deficiency of the ruthenium supported by η6-arene ligand and two chalcogenolate ligands. Two new hydrazine complexes (η6-C6H6)Ru(η1-NH2NH2)(S-2,6-C6H3Me2)2 (10a) and [(η6-C6Me6)Ru(S2C6H4)]2( μ-NH2NH2) (16) were crystallographically characterized. The observed two different coordination modes, mononuclear η1-hydrazine and binuclear μ-hydrazine, were the results of the combined steric effect of the arene and the thiolate coligands as well as the NH ... S hydrogen bonding.
