Research & Teaching Faculty

New details concerning the reactions of nitric oxide with vanadium tetrachloride

TitleNew details concerning the reactions of nitric oxide with vanadium tetrachloride
Publication TypeJournal Article
Year of Publication2004
AuthorsHayton, TW, Patrick, BO, Legzdins, P
JournalInorganic Chemistry
Volume43
Pagination7227-7233
Date PublishedNov
Type of ArticleArticle
ISBN Number0020-1669
Keywords(BUSI)-BU-T(CH2PME2)(3), (TRIMPSI)M(CO)(2)(NO) COMPLEXES M, CHLORIDE, COORDINATION-COMPOUNDS, CRYSTAL-STRUCTURE, DICHLOROTRINITROSYLVANADIUM, IR-SPECTRUM, NITROSYLS, REACTIVITY, TRIMPSI
Abstract

The slow addition of NO to a CCl4 solution Of VCl4 reproducibly forms the known polymer [V(NO)(3)Cl-2](n) as a dark brown powder. Treatment of a CH2Cl2 suspension of [V(NO)(3)Cl-2], with excess THF generates mer-(THF)(3)V(NO)Cl-2 (1) which can be isolated as an orange crystalline material in 55% yield. The reaction of 1 with excess MeCN or 1 equiv of trimpsi (trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)) provides yellow-orange (MeCN)(3)V(NO)Cl-2.MeCN (2.MeCN) and yellow (trimpsi)V(NO)Cl-2 (3), respectively. A black, crystalline complex formulated as [NO][VCl5] (4) is formed by the slow addition of NO to neat VCl4 or by the reaction of excess CINO with neat VCl4. Complex 4 is extremely air- and moisture-sensitive, and IR spectroscopy suggests that in solutions and in the gas phase it dissociates back into VCl4 and CINO. Reaction of 4 with excess [NEt3(CH2Ph)]Cl generates [NEt3(CH2Ph)](2)[VCl6].2CH(2)Cl(2) (5.2CH(2)Cl(2)), which can be isolated as deep-red crystals in 51% yield. All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of 1, 2.MeCN, and 5.2CH(2)Cl(2) have been established by single-crystal X-ray diffraction analyses.

URL<Go to ISI>://000224792900049