Nucleophilic attack on olefins co-ordinated to platinum. Part 2. Stabilities of 2-ammonioethanide ? adducts and of five-co-ordinate complexes
作者:Ibrahim M. Al-Najjar、Michael Green
DOI:10.1039/dt9790001651
日期:——
+ PtII(η-C2H4)⇌σ-amCH2H2Pt, and are discussed in terms of the nature of am, the attacking amine. Lack of bulk in am is more important than its basicity, π effects also being relevant. Data are also given on an equilibrium in which five-co-ordinate complexes are produced, e.g. py +[PtCl2(η-C2H4)(py)]⇌[PtCl2(η-C2H4)(py)2](py = pyridine). The reaction is specific to aromatic amines, which suggests that
报道了各种新的2-氨碘乙烷-铂(II)配合物(即含有amCH 2 H 2 Pt,am =胺的化合物)的制备和表征。这些已用于通过1 H nmr光谱法鉴定其他较不稳定的亲戚。nmr数据未显示复合物的稳定性。已经研究了amCH 2 H 2基团的反式标签化;在nmr时间尺度上,转位胺的交换是缓慢的。平衡常数已经测量为反应上午+铂II(η-C 2 H ^ 4)⇌ σ-amCH 2 ħ 2 Pt和在上午的性质,攻击胺来讨论。am缺乏体积比其基本性更为重要,π效应也很重要。数据被在其中五坐标复合物所产生的平衡,也给出了例如PY + [氯铂酸2(η-C 2 H ^ 4)(PY)] ⇌ [氯铂酸2(η-C 2 H ^ 4)(PY )2 ](py =吡啶)。该反应特定于芳族胺,这表明π相互作用在缔合取代中很重要。η-C的易感性2 ħ 4和Pt将II对亲核攻击进行比较,前者是较硬的酸。