کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1322010 1499850 2015 9 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Cationic iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+ and [3-(MeCN)3-3,1,2-IrC2B9H11]+: Synthesis, reactivity, and bonding. Catalysis of oxidative coupling of benzoic acid with alkynes
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Cationic iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+ and [3-(MeCN)3-3,1,2-IrC2B9H11]+: Synthesis, reactivity, and bonding. Catalysis of oxidative coupling of benzoic acid with alkynes
چکیده انگلیسی


• A general one-pot method was developed for synthesis of (arene)iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+.
• The (arene)iridacarboranes catalyze the oxidative coupling of benzoic acid with diphenylacetylene giving isocoumarin.
• DFT calculations suggested that the selectivity of catalytic reactions is determined by the electronic properties of ligand.

(Arene)iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+ (arene = benzene (1a), toluene (1b), o-xylene (1c), m-xylene (1d), durene (1e)) were synthesized by reaction of [(cod)IrCl]2 with Tl[Tl(η-7,8-C2B9H11)] with the subsequent treatment of the anion [3-(cod)-3,1,2-IrC2B9H11]− formed by arenes in refluxing trifluoroacetic acid. Cation 1a reacts with acetonitrile giving complex [3-(MeCN)3-3,1,2-IrC2B9H11]+ (2). Reactions of 2 with Cp– anions and arenes afford the cyclopentadienyl and arene derivatives 3-(η-C5H4R)-3,1,2-IrC2B9H11 (R = H (3a), C(O)Me (3b)) and [3-(arene)-3,1,2-IrC2B9H11]+ (arene = mesitylene (1f), [2,2]paracyclophane (1g)). The structures of 1ePF6 and 2BF4 were determined by X-ray diffraction. According to energy decomposition analysis, the metal-benzene bonding in the iridium cation 1a is stronger than in the rhodium analog [3-(η-C6H6)-3,1,2-RhC2B9H11]+ but weaker than in [(C5R5)Ir(C6H6)]2+. In the presence of Ag2CO3, iridacarboranes 1a and 2 catalyze the oxidative coupling of benzoic acid with diphenylacetylene selectively giving 3,4-diphenylisocoumarin in 40–50% yields. In contrast, the reactions catalyzed by [3,3-Cl2-4-SMe2-3,1,2-IrC2B9H10]2 and [CpIrI2]2 afford only 1,2,3,4-tetraphenylnaphthalene in 10 and 35% yields, respectively. The iridium catalyzed decarboxylation of benzoic acid was analyzed by DFT calculations.

(Arene)iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+ were synthesized by reaction of [(cod)IrCl]2 with Tl[Tl(η-7,8-C2B9H11)] with the subsequent refluxing in trifluoroacetic acid in the presence of arenes. Their catalytic activity in the oxidative coupling of benzoic acid with alkynes is discussed.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 793, 15 September 2015, Pages 232–240
نویسندگان
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