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首页> 外文期刊>Chemistry: A European journal >A synthetic breakthrough into an unanticipated stability regime: A series of isolable complexes in which C-6, C-8, C-10, C-12, C-16, C-20, C-24, and C-28 polyynediyl chains span two platinum atoms
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A synthetic breakthrough into an unanticipated stability regime: A series of isolable complexes in which C-6, C-8, C-10, C-12, C-16, C-20, C-24, and C-28 polyynediyl chains span two platinum atoms

机译：突破意外稳定性的合成突破：一系列可分离的络合物，其中C-6，C-8，C-10，C-12，C-16，C-20，C-24和C-28聚炔二链跨越两个铂原子

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The reaction of trans-[PtCl-(p-tol){P-tol)(3)}(2)] (PtCl) and H(C equivalent to C)(2)H (cat. CuI, HNEt2) gives PtC4H (82%), which can be cross-coupled with excess HC equivalent to CSiEt3 (acetone, O-2, CuCl/TMEDA; Hay conditions) to yield PtC6Si (77%). The addition of nBu(4)N(+)F(-) in wet acetone gives PtC6H (84%), and further addition of ClSiMe3 (F- scavenger) and excess HC equivalent to CSiEt3 (Hay conditions) yields PtC8Si (23%). Similar cross-coupling reactions of PtCxH (generated in situ for x > 6) and excess H(C equivalent to C)(2)SiEt3 give a) x=4, PtC8Si (29%), PtC12Si (30%), and PtC16Si (1%); b) x=6, PtC10Si (59%) and PtC14Si (7%); c) x=8, PtC12Si (42%); and d) x=10, PtC14Si (20%). Hay homocoupling reactions of PtC4H, PtC6H, PtC8H, and PtC10H give PtC8Pt, PtC12Pt, PtC16Pt, and PtC20Pt (88-70%), but PtC12H decomposes too rapidly. However, when PtC12Si and PtC14Si are subjected to Hay conditions, protodesilylation occurs in the presence of the oxidizing agent and PtC24Pt (36%) and PtC28Pt (51%) are isolated. Reactions of PtC6H and PtC10H with PtCl (CuI, HNEt2) give PtC6Pt (56%) and PtC10Pt (84%). The effect of the chain lengths in PtCxPt upon thermal stabilities (> 200 degrees C for x <= 20), 20), IR nu(C equivalent to C) patterns (progressively more bands), colors (yellow to orange to deep red), UV/Vis spectra (progressively red-shifted and more intense bands with epsilon > 400000 M-1 cm(-1)), redox properties (progressively more difficult oxidations), and NMR spectra (many monotonic trends) are analyzed, including implications for the sp carbon allotrope carbyne. Whereas all other dodecaynes and tetradecaynes rapidly decompose at room temperature, PtC24Pt and PtC28Pt remain stable at > 140 degrees C. Crystal structures of PtCxSi (x=6, 8, 10) and PtCxPt (x=6, 8, 10, 12) have been determined.
机译：反式-[PtCl-（对甲苯基）{P-甲苯基（3）}（2）]（PtCl）与H（C等同于C）（2）H（Cat。CuI，HNEt2）的反应生成PtC4H （82％），可以将其与相当于CSiEt3的过量HC（丙酮，O-2，CuCl / TMEDA; Hay条件）交叉偶联，得到PtC6Si（77％）。在湿丙酮中添加nBu（4）N（+）F（-）得到PtC6H（84％），然后进一步添加ClSiMe3（F-清除剂）和相当于CSiEt3的过量HC（Hay条件），得到PtC8Si（23％ ）。 PtCxH（对于x> 6原位生成）和过量的H（C等于C）（2）SiEt3的相似交叉偶联反应得到a）x = 4，PtC8Si（29％），PtC12Si（30％）和PtC16Si （1％）; b）x = 6，PtC10Si（59％）和PtC14Si（7％）; c）x = 8，PtCl2Si（42％）; d）x ＝ 10，PtCl 4 Si（20％）。 PtC4H，PtC6H，PtC8H和PtC10H的干草均偶联反应产生PtC8Pt，PtC12Pt，PtC16Pt和PtC20Pt（88-70％），但PtC12H分解得太快。但是，当将PtC12Si和PtC14Si置于Hay条件下时，在氧化剂的存在下发生原甲硅烷基化反应，并分离出PtC24Pt（36％）和PtC28Pt（51％）。 PtC6H和PtC10H与PtCl（CuI，HNEt2）的反应得到PtC6Pt（56％）和PtC10Pt（84％）。 PtCxPt中链长对热稳定性（对于x <= 20，> 200摄氏度），20，IR nu（C等于C）模式（逐渐增加的条带），颜色（黄色到橙色到深红色）的影响，UV / Vis光谱（渐进红移且ε> 400000 M-1 cm（-1）时出现更强的带），氧化还原特性（渐进地更难氧化）和NMR光谱（许多单调趋势）进行了分析，包括用于sp碳同素异形体卡宾。而所有其他十二碳和十四碳在室温下会迅速分解，而PtC24Pt和PtC28Pt在> 140摄氏度时仍保持稳定。PtCxSi（x = 6、8、10）和PtCxPt（x = 6、8、10、12）的晶体结构被确定。

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