Thiosemicarbazone platinacycles with tertiary phosphines. Preparation of novel heterodinuclear platinum-tungsten complexes

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• 作者：Darí ; o Lata^a ; M. Teresa Pereira^a ; Juan M. Ortigueira^a ; Javier Martí ; nez^a ; Brais Berm&uacute ; dez^a ; Jes&uacute ; s J. Ferná ; ndez^b ; José ; M. Vila^a ; ^{josemanuel.vila@usc.es}
• 关键词：Platinum ; Metallation ; Thiosemicarbazone ; Phosphorus ligands ; Tungsten
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：28 June, 2012
• 卷：41
• 期：1
• 页码：30-39
• 文件大小：521 K

摘要

Treatment of thiosemicarbazones (R¹C₆H₄)C(H)NN(H)C(S)NHR² [R¹,R²: 4-Me,H (a); 4-Me,Me (b); 4-Me,Et (c); 2-Me,H (d); 2-Me,Me (e); 2-Me,Et (f)] with cis-[PtMe₂(cod)] afforded the tetranuclear platinum(II) compounds [Pt{(R¹C₆H₃)C(H)NNC(S)NHR²}]₄ (1a-1f) with the ligand as terdentate [C,N,S] after C-H activation and NH deprotonation. The reaction of 1a-1f with PPh₃ in 1:4 M ratio gave the mononuclear compounds [Pt{(R¹C₆H₃)C(H)NNC(S)NHR²}(PPh₃)] (2a-2f). Treatment of 1a-1f with large-bite diphosphines Ph₂P(CH₂)_nPPh₂ (n = 2, dppe; n = 3, dppp; n = 4, dppb) afforded the dinuclear compounds [{Pt[(R¹C₆H₃)C(H)N-N = C(S)NHR²]}₂{渭-Ph₂P(CH₂)_nPPh₂}], (3a-3f, 4a-4f, 5a-5f), with the diphosphine in a bridging mode. Similar reactions with the short-bite diphosphines Ph₂PCH₂PPh₂ (dppm) and Ph₂PC(CH₂)PPh₂ (vdpp) yielded the mononuclear compounds [Pt{(R¹C₆H₃)C(H)NNC(S)NHR²}(Ph₂PR³PPh₂-P)] (R³ = CH₂, 6a-6f; R³ = C = CH₂, 7a-7f) with the diphosphine in a monodentate coordination. Treatment of 1a-1f with [W(CO)₅(Ph₂CH₂PPh₂)] gave the heterodinuclear species [{Pt[(R¹C₆H₃)C(H)NNC(S)NHR²]}{Ph₂CH₂PPh₂W(CO)₅}] (8a-8f). The molecular structures of compounds 3e and 5c have been determined by X-ray crystal structure analysis.