Antisymbiosis. Preferential coordination of anionic oxygen versus neutral sulfur donor atoms of methylsulfanyl- or methylsulfinyl-acetato, 2-benzoato and 2-phenolato to the cis-PtII(PPh3)2 and PtII(dppe) residues
作者:Laura Battan、Serena Fantasia、Mario Manassero、Alessandro Pasini、Mirella Sansoni
DOI:10.1016/j.ica.2004.09.039
日期:2005.2
tetramethylthiourea. Substitution of L’s occurs with N,N′-diethyldithiocarbamate, which forms a very stable chelate with Pt(II). Thiourea and N,N′-dimethylthiourea also react, because they give rise to cyclometallated products [Pt(phos)2(NRC(S)NHR)]+ (R = H, CH3), with one ionised thioamido group, as revealed by an X-ray investigation of [Pt(PPh3)2(NHC(S)NH2)]+. The preference of O versus S coordination, as well as
过量的标题的相互作用配体L -与顺式-Pt(PHOS)2个部分得到化合物一- b顺- [铂(L- ø)2(膦)2 ](一,PHOS = P(PH)3 ; b,phos = 1/2 dppe),其中O-优于S-配位。这样的偏好是由相同的产品是由的过量的L-的反应获得的事实证实-与以前报道的一- d络合物[PT(L- O,S)(膦)2] +,(c,phos = PPh 3,d,phos = 1/2 dppe),由于Pt–S而不是Pt–O键断裂,螯合物开环发生。化合物a也可以通过将HL氧化加成到[Pt(PPh 3)3 ]中而获得。化合物a - d中的Pt-O键对于被Me 2 SO,吡啶和四甲基硫脲取代是稳定的。N,N'-二乙基二硫代氨基甲酸酯会取代L's ,后者与Pt(II)形成非常稳定的螯合物。硫脲和N,N′-二甲基硫脲也会发生反应,因为它们会产生一个环化金属化产物[Pt(phos)2(N RC(S)NHR)]