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Reactivity of (trimpsi)V(NO)X-2 complexes (X = Cl, Br, I; trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)). Synthesis of the first group 5 alkyl nitrosyls

TitleReactivity of (trimpsi)V(NO)X-2 complexes (X = Cl, Br, I; trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)). Synthesis of the first group 5 alkyl nitrosyls
Publication TypeJournal Article
Year of Publication2004
AuthorsHayton, TW, Patrick, BO, Legzdins, P
JournalOrganometallics
Volume23
Pagination657-664
Date PublishedFeb
Type of ArticleArticle
ISBN Number0276-7333
KeywordsCHEMISTRY, CP’M(NO)R2, CRYSTAL-STRUCTURES, DERIVATIVES, H BOND ACTIVATION, MOLYBDENUM, THERMAL-ACTIVATION, TUNGSTEN, V METAL-CARBONYLS, VANADIUM
Abstract

Treatment of (trimpsi)V(NO)Cl-2 (trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)) in NEt3 with 2 equiv each of p-toluic acid and Proton Sponge affords lemon yellow (trimpsi)V(NO)(eta(1)-O2C-4-C6H4Me)(2) (1) in 47% isolated yield. Similarly, reaction of (trimpsi)V(NO)Cl-2 with 2 equiv of AgOTf in CH2Cl2 provides lemon yellow (trimpsi)V(NO)(OTf)(2) (2) in a comparable yield. Alternatively, 2 can be obtained directly in 40% yield by treating CH2Cl2 solutions of (trimpsi)V(CO)(2)(NO) at -60 degreesC with 2 equiv of AgOTf. Likewise, both benzoyl peroxide and diphenyl disulfide are capable of oxidizing (trimpsi)V(CO)(2)(NO) under similar conditions to form (trimpsi)V(NO)X-2-type complexes, namely (trimpsi)V(NO)(O2CPh)(2) (3) and (trimpsi)V(NO)(SPh)(2) (4), respectively. The reactions of (trimpsi)V(NO)X-2 (X = Cl, Br) with Mg(CH2SiMe3)(2)(.)x(dioxane) (either 0.5 equiv or an excess) in THF afford the orange-red alkyl complexes (trimpsi)V(NO)(CH2SiMe3)X (X = Cl (5), Br (6)) in reasonable yields. Other members of this family of complexes such as (trimpsi)V(NO)(CH2CMe3)Cl (7) and (trimpsi)V(NO)(Me)Cl (8) can also be obtained by employing similar metathetical methodology, but all attempts to synthesize (trimpsi)V(NO)(alkyl)2 complexes have to date been unsuccessful. All new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1(.)1.5C(6)H(5)Me and 5(.)2C(4)H(8)O have been established by single-crystal X-ray diffraction analyses.

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