Six-membered cyclometallated derivatives of platinum(II) derived from 2-benzylpyridines. Crystal and molecular structure of [Pt(L)(Ph3P)Cl] (HL = 2-(1-methylbenzyl)pyridine) |
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| Institution: | 1. School of Mechatronic Engineering and Automation, Key Laboratory of Advanced Display and System Applications, Ministry of Education, Shanghai University, 149 Yanchang Road, Shanghai, 200072, P. R. China;2. Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, Shanghai University, 99 Shangda Road, Shanghai 200444, P. R. China;3. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, P. R. China;4. School of Chemical Engineering, Dalian University of Technology, Liaoning 116024, P.R. China;5. Institute of Molecular Functional Materials and Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, P. R. China;1. Department of Chemistry, University of North Bengal, Darjeeling 734013, India;2. Department of Chemistry, National Institute of Technology, Durgapur 713209, India;3. Department of Chemistry, Alipurduar University, Alipurduar 736122, India;4. Department of Biotechnology, University of North Bengal, Darjeeling 734013, India;1. Department of Chemistry, Northwestern University, 2045 Sheridan Road, Evanston, IL 60208, USA |
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| Abstract: | The reaction of K2PtCl4] with 2-(1-methylbenzyl)pyridine, HL, and 2-benzylpyridine, HL', affords the cyclometallated species {Pt(L)Cl}2] (1) and {Pt(L')Cl}2] (2), respectively. The chloride bridge in complex 1 can be split by neutral or anionic species to give the monomeric, Pt(L)(Ph3P)Cl], as two isomers, trans-P-Pt-C (3) and trans-P-Pt-N, (4), Pt(L)(py)Cl] (5), Pt(L)(CO)Cl] (6), Pt(L)(CNCH2SO2C6H4CH3-4)Cl] (7), Pt(L)(acac)] (Hacac = 2,4-pentanedione) (8), Pt(L)(dppm)]BF4] (dppm = bis(diphenyl-phosphino)methane) (9), Pt(L)(dppe)]BF4] (dppe = bis(diphenylphosphino)ethane) (10) and Pt(L)(dipy)]BF4](dipy = 2,2'-dipyridine) (11). Similarly, compound 2, by reaction with Ph3P, affords Pt(L')(Ph3P)Cl], as two isomers, trans-P-Pt-C (12) and trans-P-Pt-N (13). Reaction of compounds 1 or 4 with AgBF4 in acetonitrile affords Pt(L)(CH3CN)2IBF4] (14) or Pt(L)(Ph3P)-(CH3CN)]BF4] (15). From these, Pt(L)(Ph3P)2]BF4] (16), Pt(L)(Ph3P)(CO)]BF4] (17) and Pt(L)(Ph3P)(py)]BF4] (18), can be obtained by displacement of the coordinated acetonitrile. The new complexes were characterized by IR, 1H and 31P NMR and FAB-MS spectroscopic techniques. The NMR spectra at room temperature of most of the species derived from HL give evidence for the presence in solution of two diastereomers a and b. The structure of one diastereomer of complex 4 has been solved by single crystal X-ray diffraction, 4b. The platinum atom is in an almost square planar geometry with a P-Pt-N trans arrangement: Pt-N = 2.095(3), Pt-C = 1.998(4), Pt-P = 2.226(1) and Pt-Cl = 2.400(1) Å. The six-membered cyclometallated ring is in a boat conformation, with the CH3 group in an equatorial position, i.e pointing away from the metal. Attempts to obtain {Pt(L″)Cl}2] (HL″ = 2-(dimethylbenzyl)pyridine), afforded an insoluble product heavily contaminated by platinum metal; treatment of this crude material with Ph3P gave Pt(L″)(Ph3P)Cl] (19). |
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