Towards multistranded molecular wires: Syntheses, structures, and reactivities of tetraplatinum bis(polyynediyl) complexes with Pt-Cx-Pt-(P(CH2)3P)2-Pt-Cx-Pt-(P(CH2)3P)2 cores (x = 4, 6, 8)
Towards multistranded molecular wires: Syntheses, structures, and reactivities of tetraplatinum bis(polyynediyl) complexes with Pt-Cx-Pt-(P(CH2)3P)2-Pt-Cx-Pt-(P(CH2)3P)2 cores (x = 4, 6, 8)
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走向多链分子线：四铂双（聚炔二基）配合物的合成、结构和反应活性 - Pt-Cx-Pt-(P(CH2)3P)2-Pt-Cx-Pt-(P(CH2)3P)
DOI：
10.1039/c002041a
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发表时间：
2010
影响因子：
4
通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
--
作者：
Owen, Gareth R.;Gauthier, Sébastien;Weisbach, Nancy;Hampel, Frank;Bhuvanesh, Nattamai;Gladysz, John A.
反，反-（C6 F5）（p-tol 3 P）2 Pt（CC）nPt（Pp-tol 3）2（C6 F5）的反应（PtCxPt; x = 2n）和1，3-二膦Ph 2 P（CH 2）3 PPh 2（2.5当量）得到四铂络合物反式，反式-（C6 F5）Pt（CC）nPt（C6 F5）（PPh2（CH2）3Ph2P）2（C6F5）Pt（CC）nPt（C6F5）（PPh2（CH2）3Ph2P）2（[Pt′CxPt′]2; x = 4/6/8，39%/95%/81%）。测定了[Pt′ C8 Pt ′]2及其两种溶剂化物的晶体结构。这些证实了每个二膦跨越来自不同Pt（CC）nPt键的两个铂原子，与（1）1，2-二膦Ph 2 P（CH 2）2 PPh 2相反，其在与PtC 8 Pt类似的条件下得到双铂双（螯合物）顺式，顺式-（PPh 2（CH 2）2 Ph 2 P）（C6 F5）Pt（CC）4Pt（C6 F5）（PPh 2（CH 2）2 Ph 2 P）（73%）或（2）具有较长亚甲基链的α，ω-二膦，其跨越铂末端。制剂[Pt′ C4 Pt ′]2通过与PEt 3（10当量）反应而负载，得到反式，反式-（C6 F5）（Et 3 P）2 Pt（CC）2 Pt（PEt 3）2（C6 F5）。在[Pt′ C8 Pt ′]2和[Pt′ C6 Pt ′]2的一种溶剂化物中，链以77.2°-87.7°角交叉，链间最近的碳-碳距离（3.27-3.61 μ m）小于范德华半径之和。在[Pt′ C6 Pt ′]2的另一种溶剂化物中，链基本上是平行的，并且分离更大（4.96 μ m）。紫外-可见光谱显示没有特殊的电子相互作用。然而，循环伏安图表明不可逆的氧化，与PtC 6Pt和PtC 8 Pt的部分可逆氧化相反。最初形成的自由基阳离子进行快速链-链耦合。新的配合物在185 °C以上分解而不熔化。[Pt′ C8 Pt ′]2的红外光谱表明形成了一种新的富CC物质。
Reactions of trans,trans-(C6F5)(p-tol3P)2Pt(CC)nPt(Pp-tol3)2(C6F5) (PtCxPt; x = 2n) and the 1,3-diphosphine Ph2P(CH2)3PPh2 (2.5 equiv) give the tetraplatinum complexes trans, trans,trans,trans-(C6F5)Pt(CC)nPt(C6F5)(PPh2(CH2)3Ph2P)2(C6F5)Pt(CC)nPt(C6F5)(PPh2(CH2)3Ph2P)2 ([Pt′CxPt′]2; x = 4/6/8, 39%/95%/81%). Crystal structures of [Pt′C8Pt′]2 and two solvates of [Pt′C6Pt′]2 are determined. These confirm that each diphosphine spans two platinum atoms from different Pt(CC)nPt linkages, as opposed to (1) the 1,2-diphosphine Ph2P(CH2)2PPh2, which under similar conditions with PtC8Pt affords the diplatinum bis(chelate) cis,cis-(PPh2(CH2)2Ph2P)(C6F5)Pt(CC)4Pt(C6F5)(PPh2(CH2)2Ph2P) (73%) or (2) α,ω-diphosphines with longer methylene chains, which span the platinum termini. The formulation [Pt′C4Pt′]2 is supported by a reaction with PEt3 (10 equiv) to give trans,trans-(C6F5)(Et3P)2Pt(CC)2Pt(PEt3)2(C6F5). In [Pt′C8Pt′]2 and one solvate of [Pt′C6Pt′]2, the chains cross at 77.2°–87.7° angles, with the closest interchain carbon–carbon distances (3.27–3.61 Å) less than the sum of the van-der-Waals radii. In the other solvate of [Pt′C6Pt′]2, the chains are essentially parallel, and the separation is much greater (4.96 Å). UV-visible spectra show no special electronic interactions. However, cyclic voltammograms indicate irreversible oxidations, in contrast to the partially reversible oxidations of PtC6Pt and PtC8Pt. The initially formed radical cations are proposed to undergo rapid chain–chain coupling. The new complexes decompose without melting above 185 °C. With [Pt′C8Pt′]2, IR spectra indicate the formation of a new CC-rich substance.