کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1325013 1499937 2012 9 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Oxidative addition of MeI to some cyclometalated organoplatinum(II) complexes: Kinetics and mechanism
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Oxidative addition of MeI to some cyclometalated organoplatinum(II) complexes: Kinetics and mechanism
چکیده انگلیسی

New cyclometalated platinum(II) complexes [PtMe(C^N)L], 1, in which C^N = deprotonated 2-phenylpyridine (ppy), benzo[h]quinoline (bhq) or 2-(p-tolyl)pyridine (tpy) and L = PPh3 or PMePh2, were synthesized by the reaction of [PtMe(C^N)(SMe2)] with 1 equiv of L. The reaction of complexes 1 with MeI gave the cyclometalated Pt(IV) complexes [PtMe2I(C^N)L], 3. On the basis of kinetic studies, using Uv–visible spectroscopy, it was suggested that the latter oxidative addition reactions were proceeded by an SN2 mechanism. The rates of the reactions at different temperatures were measured and consistent with the proposed mechanism, large negative ΔS‡ values were found for each reaction. Besides, rate of reactions (in CHCl3) involving the PPh3 complexes [PtMe(C^N)(PPh3)], were almost 3–5 times slower than those involving the PMePh2 complexes [PtMe(C^N)(PMePh2)]. This was attributed to the electronic and steric effects of PPh3 ligand as compared with that of PMePh2 ligand which was further confirmed using density functional theory (DFT) calculations through finding approximate structures for the described complexes.

New cyclometalated platinum(II) complexes [PtMe(C^N)L] (C^N = deprotonated 2-phenylpyridine (ppy), benzo[h]quinoline (bhq) or 2-(p-tolyl)pyridine (tpy) and L = PPh3 or PMePh2) were synthesized and the kinetics and mechanism of oxidative addition of MeI to these complexes are studied.Figure optionsDownload as PowerPoint slideHighlights
► New cyclometalated platinum(II) and (IV) compounds are prepared.
► Oxidative addition of MeI to cyclometalated Pt(II) complexes is investigated.
► Kinetics and mechanisms of these oxidative addition reactions are studied.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Organometallic Chemistry - Volume 698, 1 February 2012, Pages 53–61
نویسندگان
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