Formation of P−C Bonds under Unexpectedly Mild Conditions. Phosphoryl Migration and Metal Coordination of Diphenylphosphinomethyl-oxazolines and -thiazolines

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• 作者：Roberto Pattacini ; Gü ; nter Margraf ; Abdelatif Messaoudi ; Nicola Oberbeckmann-Winter ; Pierre Braunstein
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：November 3, 2008
• 年：2008
• 卷：47
• 期：21
• 页码：9886-9897
• 全文大小：397K
• 年卷期：v.47,no.21(November 3, 2008)
• ISSN：1520-510X

文摘

The heterocycles 2-methyl-2-oxazoline (mox) and 2-methyl-2-thiazoline (mth) react with Ph₂PCl under mild conditions, in the presence of NEt₃ which promotes their phosphorylation by stabilization of their enamino tautomers mox_e and mth_e, respectively, and which also behaves as HCl scavenger. Depending on the reaction conditions, three different phosphine ligands were obtained in good yields from mox: the monophosphine Ph₂PCH₂CNCH₂CH₂O (1_ox) and the isomeric diphosphines Ph₂PCHCOCH₂CH₂NPPh₂ (2_ox) (X-ray structure) and (Ph₂P)₂CHCNCH₂CH₂O (3_ox). The formation of these ligands involves phosphoryl migration reactions, which were studied by NMR spectroscopy. The synthesis and the X-ray structures of the corresponding diphenylphosphinothiazolines Ph₂PCH₂CNCH₂CH₂S (1_th) and Ph₂CHCSCH₂CH₂NPPh₂ (2_th) are also reported but the thiazoline analog of the geminal diphosphine 3_ox was not observed. The metal complexes [Pt(3_ox-H)₂]·4CH₂Cl₂ (4·4CH₂Cl₂), [Pt(Me)I(1_ox)] (5), [Pt(Me)₂(1_ox)] (7), [Pd(dmba-C,N)(1_th)]OTf·0.25Et₂O (8·0.25Et₂O), [Pd(dmba-C,N)(1_th-H)] (9), and [9·{Pd(dmba-C,N)Cl}]·2.5C₆H₆ (10·2.5C₆H₆) have been prepared and structurally characterized by X-ray diffraction.