PPh3-Derivatives of [Pt3n(CO)6n]2鈥?/sup> (n = 2鈥?) Chini鈥檚 Clusters: Syntheses, Structures, and 31P NMR Studies
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- 作者：Iacopo Ciabatti ; Cristina Femoni ; Maria Carmela Iapalucci ; Giuliano Longoni ; Tatiana Lovato ; Stefano Zacchini
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：April 15, 2013
- 年：2013
- 卷：52
- 期：8
- 页码：4384-4395
- 全文大小：465K
- 年卷期：v.52,no.8(April 15, 2013)
- ISSN：1520-510X
文摘
The reaction of the [Pt3n(CO)6n]2鈥?/sup> (n = 2鈥?) Chini鈥檚 clusters with increasing amounts of PPh3 has been investigated in detail by combined FT-IR, 31P{1H} NMR, and electrospray ionization-mass spectrometry (ESI-MS) studies, showing that up to three CO ligands are gradually substituted by PPh3, resulting in isonuclear phosphine-substituted anionic clusters of general formula [Pt3n(CO)6n鈭?i>x(PPh3)x]2鈥?/sup> (n = 2鈥?; x = 1鈥?). Further addition of PPh3 results in the elimination of the neutral Pt3(CO)3(PPh3)3 species and formation of lower nuclearity anionic clusters. [Pt12(CO)22(PPh3)2]2鈥?/sup> and [Pt9(CO)16(PPh3)2]2鈥?/sup> have been structurally characterized, and they maintain the trigonal prismatic structures of the parent homoleptic clusters, with the two PPh3 ligands bonded to different external Pt3-triangles in relative cis-position. Conversely, the crystal structure of [Pt6(CO)10(PPh3)2]2鈥?/sup> shows that its metal cage is transformed from trigonal prismatic to trigonal antiprismatic after CO/PPh3 exchange.