کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1307655 975149 2011 13 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N3)(PMe3)3 with azide as the oxidant
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N3)(PMe3)3 with azide as the oxidant
چکیده انگلیسی

Addition of excess trimethylphosphine and a halide source to a solution of W(CO)(acac)2(η2-L) (L = NCPh and OCMe2) leads to displacement of L and one acetylacetonate chelate to produce electron-rich, seven-coordinate complexes of the formula W(CO)(acac)(X)(PMe3)3 (X = Cl, Br, and I). Use of NaN3 instead of a halide source leads primarily to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe3)3]+. Heating [W(NH)(acac)(PMe3)3]+ in aromatic isocyanates at high temperature results in isocyanate insertion into the NH imido bond to form new C–N bonds. An alternate route to related imido complexes involves heating [W(O)(acac)(PMe3)3]+ with phenyl isocyanate at high temperatures to yield the substituted imido complex [W(NPh)(acac)(PMe3)3]+.

Addition of excess trimethylphosphine and a halide source to W(CO)(acac)2(η2-OCMe2) leads to production of W(CO)(acac)(X)(PMe3)3. Reaction with NaN3 leads to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe3)3]+. Heating [W(NH)(acac)(PMe3)3]+ in aromatic isocyanates results in isocyanate insertion into the NH imido bond to form new C–N bonds.Figure optionsDownload as PowerPoint slideResearch highlights
► Electron-rich, seven-coordinate tungsten complexes.
► Tungsten–imido complex formation from azide.
► Isocyanate insertion.
► C–N bond formation.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Inorganica Chimica Acta - Volume 369, Issue 1, 15 April 2011, Pages 19–31
نویسندگان
, , , ,