339567-15-6Relevant articles and documents
C-H activation in phosphonium salts promoted by platinum(II) complexes
Falvello, Larry R.,Fernández, Susana,Larraz, Carmen,Llusar, Rosa,Navarro, Rafael,Urriolabeitia, Esteban P.
, p. 1424 - 1436 (2001)
The reaction of PtCl2(NCPh)2 with the bis-phosphonium salts {[R2PhPCH2]2C(O)}Cl2 (R2 = Ph2, PhEt, Et2) (1:1 molar ratio) in refluxing 2-methoxyethanol affords the C,C-orthometalated complexes [PtCl2(C6H4-2-PR2 C(H)C(O)CH2PPhR2)] (R2 = Ph2 1a, PhEt 1b, Et2 1c). The reaction of PtCl2 with the bis-phosphonium salt {[Ph3PCH2]2C(O)} Cl2 (1:1 molar ratio) gives {[Ph3PCH2]2C(O)}[PtCl4], 2, while treatment of PtCl2 with the perchlorate salts {[R2PhPCH2]2C(O)}(ClO4)2 (1:1 molar ratio) results in the formation of the cationic dinuclear orthometalated derivatives [Pt(μ-Cl)(C6H4-2-PR2C(H)C(O)CH2PP hR2)]2(ClO4)2 (R2 = Ph2 3a, PhEt 3b, Et2 3c). The cycloplatination of the bis-phosphonium salts to give the C,C-orthometalated derivatives implies two C-H bond activation processes at two types of carbon atoms, one arylic and one alkylic. The reaction of PtCl2(NCPh)2 or PtCl2 with the allylphosphonium salts [PhR2PCH2CH=CH2]Cl (R2 = Ph2, Me2) or [Ph3PCH2CH=CHMe]Cl (1:1 molar ratio) in refluxing 2-methoxyethanol gives the orthometalated vinyl-phosphonium derivatives [PtCl2(C6H4-2-PR2-η2- E-C(H)=C(H)CH3)] (R2 = Ph2 4a, Me2 4b) or [PtCl2(C6H4-2-PPh2-η2 -E-C(H)=C(H)CH2CH3)], 7, respectively, while the reaction of PtCl2 with [Ph3PCH2-CH=CH2]ClO4 (1:1 molar ratio) gives the η2-olefin-bonded derivative [Cl3Pt(η2-CH2=CH-CH2 PPh3)], 5. The reaction of [Ph3PCH2CH=CHPh]Cl with PtCl2 (1:1 molar ratio, 2-methoxyethanol, reflux) gives an easily separable mixture of products: the η2-olefin-bonded [Cl3Pt(η2-CHPh=CH-CH2PPh3)], 8, and the orthometalated [PtCl2(C6H4-2-PPh2-η2 -E-C(H)=C(H)CH2Ph)], 9, while the reaction of [Ph3PCH2CMe=CH2]Cl with PtCl2 (1:1 molar ratio) gives a mixture of the cycloplatinated [PtCl2(C6H4-2-PPh2-η2 -C(H)-CMe2)], 10, and the isomerized vinyl-phosphonium salt [Ph3P-C(H)=CMe2]Cl, 11. The synthesis of complexes 4, 7, 9, and 10 implies the activation of one C(aryl)-H bond (instead of the more active methylene group adjacent to the phosphonium unit P-CH2) and the rearrangement of the allyl group into a vinyl group by 1,3-prototropic shift, this shift being produced in the absence of external base. The complexes 4a·CH2Cl2 and 8 have been characterized by X-ray diffraction methods.
