کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
10569618 | 974158 | 2013 | 22 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Expansion and contraction: Shaping the porphyrin boundary via diradical reactivity
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی معدنی
پیش نمایش صفحه اول مقاله
چکیده انگلیسی
⺠Approach to periphery modification centered on the application of diradicals generated through unique diyne-ene and diazo-keto functionalization at the β,βâ²-position of the macrocycle. ⺠Diradical adds across the adjacent phenyl rings of the meso-positions to extend the aromaticity across three rings. ⺠Dione or diazo-keto functionalization and subsequent reaction with nucleophiles in the presence of Ag+, generates acetals that lead to modified chemical properties additional reactivity potential at the periphery - diazoketochlorin photolysis leads to rapid N2 extrusion and initial carbene formation. ⺠Wolff ring-contracted ketene, is detectable, demonstrating that the out-of-plane electronic configuration is initially generated and reacts to give the nucleophile-quenched species, as well as relaxing to form exocyclic ring addition and other radical-based products. ⺠Synthetic opportunities to markedly modulate macrocycle electronic structure in a highly asymmetric manner to form truly distinct porphyrinoid constructs.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Coordination Chemistry Reviews - Volume 257, Issue 2, 15 January 2013, Pages 599-620
Journal: Coordination Chemistry Reviews - Volume 257, Issue 2, 15 January 2013, Pages 599-620
نویسندگان
Leigh J.K. Boerner, David. F. Dye, Tillmann Köpke, Jeffrey M. Zaleski,