Dipartimento di Chimica Industriale "Toso Montanari" , Università di Bologna , Viale Risorgimento 4 , 40136 Bologna , Italy.
Inorg Chem. 2018 Jul 2;57(13):7578-7590. doi: 10.1021/acs.inorgchem.8b00447. Epub 2018 Jun 11.
The reactions of [Pt(CO)] with CH(PPh) (dppm), CH═C(PPh) (P^P), and Fe(CHPPh) (dppf) proceed via nonredox substitution and result in the heteroleptic Chini-type clusters [Pt(CO)(dppm)], [Pt(CO)(P^P)], and [Pt(CO)(dppf)], respectively. Conversely, the reactions of [Pt(CO)] with PhP(CH)PPh (dppb) and PhPC≡CPPh (dppa) can be described as redox fragmentation that afford the neutral complexes Pt(dppb), Pt(CO)(dppa), and Pt(CO)(PPh)(C≡CPPh)(dppa). The oxidation of [Pt(CO)(dppm)] results in its oligomerization to yield the larger heteroleptic Chini-type clusters [Pt(CO)(dppm)], [Pt(CO)(dppm)], and [Pt(CO)(dppm)] (for the latter there is only IR spectroscopic evidence). All the clusters were characterized by means of IR and P NMR spectroscopies and electrospray ionization mass spectrometry. Moreover, the crystal structures of [NEt][Pt(CO)(dppm)]·CHCN, [NEt][Pt(CO)(dppm)]·2CHCN·2dmf, [NEt][Pt(CO)(dppm)]·4dmf, [NEt][Pt(CO)(dppf)]·2CHCN, Pt(CO)(dppa)·0.5CHCN, Pt(CO)(PPh)(C≡CPPh)(dppa)·2thf, and Pt(dppb) were determined by single-crystal diffraction (dmf = dimethylformamide; thf = tetrahydrofuran).
[Pt(CO)]与 CH(PPh) (dppm)、CH═C(PPh) (P^P) 和 Fe(CHPPh) (dppf)的反应通过非氧化还原取代进行，分别生成了杂核奇尼型簇[Pt(CO)(dppm)]、[Pt(CO)(P^P)]和[Pt(CO)(dppf)]。相反，[Pt(CO)]与 PhP(CH)PPh (dppb)和 PhPC≡CPPh (dppa)的反应可以描述为氧化还原断裂，生成中性配合物 Pt(dppb)、Pt(CO)(dppa)和 Pt(CO)(PPh)(C≡CPPh)(dppa)。[Pt(CO)(dppm)]的氧化导致其聚合生成更大的杂核奇尼型簇[Pt(CO)(dppm)]、[Pt(CO)(dppm)]和[Pt(CO)(dppm)]（对于后者，只有红外光谱证据）。所有的簇都通过红外和磷 NMR 光谱以及电喷雾电离质谱进行了表征。此外，[NEt][Pt(CO)(dppm)]·CHCN、[NEt][Pt(CO)(dppm)]·2CHCN·2dmf、[NEt][Pt(CO)(dppm)]·4dmf、[NEt][Pt(CO)(dppf)]·2CHCN、Pt(CO)(dppa)·0.5CHCN、Pt(CO)(PPh)(C≡CPPh)(dppa)·2thf 和 Pt(dppb)的晶体结构通过单晶衍射确定（dmf = 二甲基甲酰胺；thf = 四氢呋喃）。
