کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1307655 | 975149 | 2011 | 13 صفحه PDF | دانلود رایگان |
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.
Journal: Inorganica Chimica Acta - Volume 369, Issue 1, 15 April 2011, Pages 19–31