Reactivity of (trimpsi)V(NO)X₂Complexes (X = Cl, Br, I; trimpsi =^tBuSi(CH₂PMe₂)₃). Synthesis of the First Group 5 Alkyl Nitrosyls

Abstract

Treatment of (trimpsi)V(NO)Cl2 (trimpsi = tBuSi(CH2PMe2)3) in NEt3 with 2 equiv each of p-toluic acid and Proton Sponge affords lemon yellow (trimpsi)V(NO)(η1-O2C-4-C6H4Me)2 (1) in 47% isolated yield. Similarly, reaction of (trimpsi)V(NO)Cl2 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 °C 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)X2-type complexes, namely (trimpsi)V(NO)(O2CPh)2 (3) and (trimpsi)V(NO)(SPh)2 (4), respectively. The reactions of (trimpsi)V(NO)X2 (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 1·1.5C6H5Me and 5·2C4H8O have been established by single-crystal X-ray diffraction analyses.

Benzonitrile Extrusion from Molybdenum(IV) Ketimide Complexes Obtained via Radical C−E (E = O, S, Se) Bond Formation: Toward a New Nitrogen Atom Transfer Reaction

“…The oxidation of metal complexes by benzoyl peroxide as a route to metal benzoate derivatives has been employed by Legzdins to synthesize a bisbenzoate of vanadium from a corresponding dicarbonyl . Digold(II) benzoate systems similarly have been obtained from digold(I) precursors by oxidation with benzoyl peroxide .…”

Synthesis, structure, immobilization and solid-state NMR of new dppp- and tripod-type chelate linkers

“…For example, the silicon and tin versions of triphos, MeSi(CH 2 PPh 2 ) 3 and MeSn(CH 2 PPh 2 ) 3 , are known, and their Rh(I) and Ru(II) coordination chemistry has been explored [19]. Recently, in addition the tridentate ligand t BuSi(CH 2 PMe 2 ) 3 , and the reactivity of vanadium complexes thereof, has been studied [20], but again no alkoxy derivative is known.…”

Physicochemical Factors That Influence the Deoxygenation of Oxyanions in Atomically Precise, Oxygen-Deficient Vanadium Oxide Assemblies

“…Further support for formation of the NO adduct was obtained through IR spectroscopy; a transition centered at 1537 cm –1 was observed, resembling values previously reported for vanadium complexes with a nitric oxide ligand (Figure S8). , …”

“…Further support for formation of the NO adduct was obtained through IR spectroscopy; a transition centered at 1537 cm −1 was observed, resembling values previously reported for vanadium complexes with a nitric oxide ligand (Figure S8). 41,42 We hypothesized that NO removal from the crude reaction mixture, via the addition of a NO-trapping agent [e.g., cobalt(II) tetraphenylporphyrin, CoTPP], should disfavor the formation of complex 3-V 6 O 6 NO 1− . 43−45 Therefore, NO 2 − was added to a mixture of 1-V 6 O 6 1− and CoTPP and analyzed by electronic absorption spectroscopy (Figure 2; see Figure S9 2− (Figure 2 and Scheme 1, left).…”