Reactivity Study of the Bis(phosphine)-Stabilized Antimony(I) Cation

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2024-12-11 DOI:10.1021/acs.inorgchem.4c04257

Nilanjana Mukherjee, Vikas Kumar, Cem B. Yildiz, Moumita Majumdar

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引用次数: 0

Abstract

The 5,6-Bis(diisopropylphosphino)acenaphthene L-stabilized Sb(I) cationic compound [LSb][OTf] (OTf = CF₃SO₃) 1 possessing two lone pairs of electrons on the Sb(I) center showed nucleophilic behavior toward methyl trifluoromethanesulfonate forming the oxidized product [LSbMe][OTf]₂ 2 (OTf = CF₃SO₃). Reaction of compound 1 with Lewis acids such as GaCl₃ and AlBr₃ led to changes in the counteranions only giving products [LSb][GaCl₄] 3 and [LSb][SbBr₄] 4, respectively. A metathesis reaction was observed when compound 1 was reacted with PI₃. The Sb(I) cation in 1 underwent the metathesis reaction with the P(I) cation, forming the more stable product [LP][OTf] 5. The Sb(I) center in 1 was completely oxidized to Sb(V) by reacting with two equivalents of o-chloranil to give the Bis(phosphine)-stabilized Bis(perchloro catecholato)stibonium cation [L(O₂C₆Cl₄)₂Sb][OTf] 6. Both compounds 1 and 6 were employed as proof-of-concept Lewis acid catalysts for the hydrosilylation of p-methyl benzaldehyde. All the compounds were characterized using single-crystal X-ray diffraction analysis, multinuclear nuclear magnetic resonance spectroscopy, mass spectrometry, and absorbance spectroscopy. Density functional theory calculations were performed on the relevant compounds.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.