کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1322375 1499879 2014 9 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Reactivity of a dichlorophosphido complex. Nucleophilic substitution reactions at metal coordinated phosphorus
ترجمه فارسی عنوان
واکنش یک ترکیب دیکلوفوفسیدو واکنش های جایگزین نوکلئوفیلیک در فسفر هماهنگ فلزی
کلمات کلیدی
فسفینیدین، آلکسی فسفینیدین، جایگزینی نوکلئوفیلیک، سنتز متمرکز بر فلز
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
چکیده انگلیسی


• Facile nucleophilic substitution at metal bound phosphorus.
• The first cationic alkoxy and aryloxyphosphinidenes.
• A computational study on the role of heteroatom substituents in stabilizing cationic phosphinidene complexes.

Reaction of the dichlorophosphido complex [Cp*Mo(CO)3(PCl2)] (1) with AlCl3 leads to the bimetallic bridging P2Cl3 complex [{Cp*Mo(CO)3}2(μ-P2Cl3)][AlCl4] (2), which is formed via a Lewis-acid assisted nucleophilic substitution reaction, and not via a chlorophosphinidene intermediate. A similar reaction with external nucleophile PPh3 leads to [Cp*Mo(CO)3(P(Cl)PPh3)][AlCl4] (3), which can be viewed as a phosphine coordinated chlorophosphinidene complex. Addition of two equivalents each of PPh3 and AlCl3 leads a double chloride displacement, and formation of the known triphosphenium salt [Ph3PPPPh3][AlCl4]. In this reaction the dichlorophosphido complex effectively act as a source of P+. Reaction of 1 with alkoxides leads to alkoxyphosphido complexes [Cp*Mo(CO)3{P(OR)Cl}] (R = p-t-butyl phenoxy, menthoxy). These complexes serve as precursors to transient alkoxy phosphinidenes [Cp*Mo(CO)3{POR}]+, which can be trapped with alkynes. A computational study on the chloro, alkoxy, and related amino and alkyl phosphinidenes shows that chloro and alkoxy phosphinidenes have minimal π-donation to P from Cl or OR, in contrast to stable aminophosphinidenes, which have significant N to P π-donation.

Attempted chloride abstraction from a molybdenum PCl2 complex leads to nucleophilic substitution and P–P bond formation, but not to a chlorophosphinidene. The PCl2 complex does serves as a precursor to alkoxyphosphido complexes, which can be converted to alkoxy phosphinidene complexes via chloride abstraction.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 761, 1 July 2014, Pages 84–92
نویسندگان
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