Peripherally-metallated porphyrins: meso-n1-porphyrinyl-platinum(II) complexes of 5,15-diaryl- and 5,10,15-triarylporphyrins
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Description
Attempted metathesis reactions of peripherally-metallated meso-η1-porphyrinylplatinum(II) complexes such as trans-[PtBr(NiDPP)(PPh3)2] (H2DPP = 5,15-diphenylporphyrin) with organolithium reagents fail due to competitive addition at the porphyrin ring carbon opposite to the metal substituent. This reaction can be prevented by using 5,10,15-triarylporphyrins, e.g. 5,10,15-triphenylporphyrin (H2TrPP) and 5-phenyl-10,20-bis(3’,5’-di-t-butylphenyl)porphyrin (H2DAPP) as substrates. These triarylporphyrins are readily prepared using the method of Senge and co-workers by addition of phenyllithium to the appropriate 5,15-diarylporphyrins, followed by aqueous protolysis and oxidation. They are convenient, soluble building blocks for selective substitutions and subsequent transformations at the remaining free meso carbon. The sequence of bromination, optional central metallation and oxidative addition of Pt(0) tris(phosphine) complexes generates the organoplatinum porphyrins in high overall yields. The bromo ligand on the Pt(II) centre can be substituted by alkynyl nucleophiles, including 5-ethynylNiDPP, to form the first examples of meso-η1-porphyrinylplatinum(II) complexes with a second Pt-C bond. The range of porphyrinylplatinum(II) bis(tertiary phosphine) complexes was extended to the triethylphosphine analogues, by oxidative addition of H2TrPPBr to Pt(PEt3)3, and the initially-formed cis adduct is only slowly thermally transformed to trans-[PtBr(H2TrPP)(PEt3)2] 16. The molecular structures of NiDAPP 9b, trans-[Pt(NiDPP)(C2NiDPP)(PPh3)2] 14 and 16 were determined by X-ray crystallography.
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ID Code: | 1014 |
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Item Type: | Contribution to Journal (Journal Article) |
Refereed: | Yes |
Measurements or Duration: | 13 pages |
Keywords: | Crystal Structure, Organometallic, Phosphine, Platinum, Porphyrin |
DOI: | 10.1142/S1088424602000828 |
ISSN: | 1088-4246 |
Pure ID: | 34077792 |
Divisions: | Past > QUT Faculties & Divisions > Faculty of Science and Technology Past > Schools > School of Physical & Chemical Sciences Past > QUT Faculties & Divisions > Science & Engineering Faculty Current > Research Centres > Australian Research Centre for Aerospace Automation |
Copyright Owner: | Consult author(s) regarding copyright matters |
Copyright Statement: | This work is covered by copyright. Unless the document is being made available under a Creative Commons Licence, you must assume that re-use is limited to personal use and that permission from the copyright owner must be obtained for all other uses. If the document is available under a Creative Commons License (or other specified license) then refer to the Licence for details of permitted re-use. It is a condition of access that users recognise and abide by the legal requirements associated with these rights. If you believe that this work infringes copyright please provide details by email to qut.copyright@qut.edu.au |
Deposited On: | 12 Apr 2005 00:00 |
Last Modified: | 31 Mar 2024 09:33 |
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