کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1325203 977374 2011 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Cyclometalated complexes derived from calix[4]arene bisphosphites and their catalytic applications in cross-coupling reactions
کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Cyclometalated complexes derived from calix[4]arene bisphosphites and their catalytic applications in cross-coupling reactions
چکیده انگلیسی

Palladium and platinum dichloride complexes of a series of symmetrically and unsymmetrically substituted 25,26;27,28-dibridged p-tert-butyl-calix[4]arene bisphosphites in which two proximal phenolic oxygen atoms of p-tert-butyl- or p-H-calix[4]arene are connected to a P(OR) (R = substituted phenyl) moiety have been synthesized. The palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C–C or C–H bond scission. An example of cycloplatinated complex is also reported. The complexes have been characterized by NMR spectroscopic and single crystal X-ray diffraction studies. During crystallization of the palladium dichloride complex of a symmetrically substituted calix[4]arene bisphosphite in dichloromethane, insertion of oxygen occurs into the Pd–P bond to give a P,O-coordinated palladium dichloride complex. The calix[4]arene framework in these bisphosphites and their metal complexes adopt distorted cone conformation; the cone conformation is more flattened in the metal complexes than in the free calix[4]arene bisphosphites. Some of these cyclometalated complexes proved to be active catalysts for Heck and Suzuki C–C cross-coupling reactions but, on an average, the yields are only modest.

Palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C–C or C–H bond scission.Figure optionsDownload as PowerPoint slideHighlights
► Synthesis of palladium and platinum dichloride complexes of calix[4]arene bisphosphites.
► Cyclometalation in calix[4]arene bisphosphite complexes by C–C or C–H bond scission.
► Use of cyclometalated complexes as moderately effective catalysts for Suzuki and Heck coupling.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 696, Issue 20, 1 October 2011, Pages 3169–3179
نویسندگان
, , , ,