Macrocyclic Complexes Derived from Four cis ‐L 2 Pt Corners and Four Butadiynediyl Linkers; Syntheses, Electronic Structures, and Square versus Skew Rhombus Geometries
Macrocyclic Complexes Derived from Four cis ‐L 2 Pt Corners and Four Butadiynediyl Linkers; Syntheses, Electronic Structures, and Square versus Skew Rhombus Geometries
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由四个顺式 -L 2 Pt 角和四个丁二炔二基连接体衍生的大环配合物；
DOI：
10.1002/chem.202100305
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
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作者：
Collins, Brenna K.;Clough Mastry, Melissa;Ehnbom, Andreas;Bhuvanesh, Nattamai;Hall, Michael B.;Gladysz, John A.
将丙二酸二烷基酯衍生的1，3-二膦R2 C（CH 2 PPh 2）2（R=a，Me;B，Et;c，n-Bu;d，n-Dec;e，Bn;f，p-tolCH 2）与（p-tol 3 P）2 PtCl 2或反式-（p-tol 3 P）2 Pt（（C = C）2 H）2组合，得到螯合物顺式-（R2 C（CH 2 PPh 2）2）PtCl 2（2 a-f，94- 69%）或顺式-（R2 C（CH 2 PPh 2）2）Pt（（C = C）2 H）2（3 a-f，97- 54%）。络合物3a-dare也可从2a-d和过量的1，3-丁二炔在CuI（cat.）和过量的HNEt 2（87- 65%）。在类似条件下，2和3反应得到标题化合物[（R2 C（CH 2 PPh 2）2）[Pt（C = C）2]4（4 a-f; 89- 14%（64% avg）），其中铵盐如副产物[H2 NEt 2]+Cl−难以除去。4a，b的晶体结构显示为斜菱形，而不是正方形Pt 4几何形状。4 a-的NMR和IR性质与单铂或双铂模型化合物相似。然而，循环伏安法仅给出不可逆氧化。与单铂或Pt（C = C）2 Pt物质相比，紫外可见光谱显示出更强和红移的谱带。与时间相关的DFT计算定义了所涉及的跃迁和主轨道。静电势表面图显示强烈的负Pt 4C 16核心，可能促进铵阳离子结合。计算探讨了Pt 3C 12和Pt 5C 20同系物的类似电子性质和选定的平衡。
The dialkyl malonate derived 1,3‐diphosphines R2C(CH2PPh2)2(R=a, Me;b, Et;c,n‐Bu;d,n‐Dec;e, Bn;f,p‐tolCH2) are combined with (p‐tol3P)2PtCl2ortrans‐(p‐tol3P)2Pt((C≡C)2H)2to give the chelatescis‐(R2C(CH2PPh2)2)PtCl2(2 a–f, 94–69 %) orcis‐(R2C(CH2PPh2)2)Pt((C≡C)2H)2(3 a–f, 97–54 %). Complexes3 a–dare also available from2 a–dand excess 1,3‐butadiyne in the presence of CuI (cat.) and excess HNEt2(87–65 %). Under similar conditions,2and3react to give the title compounds [(R2C(CH2PPh2)2)[Pt(C≡C)2]4(4 a–f; 89–14 % (64 % avg)), from which ammonium salts such as the co‐product [H2NEt2]+Cl−are challenging to remove. Crystal structures of4 a,bshow skew rhombus as opposed to square Pt4geometries. The NMR and IR properties of4 a–fare similar to those of mono‐ or diplatinum model compounds. However, cyclic voltammetry gives only irreversible oxidations. As compared to mono‐platinum or Pt(C≡C)2Pt species, the UV‐visible spectra show much more intense and red‐shifted bands. Time dependent DFT calculations define the transitions and principal orbitals involved. Electrostatic potential surface maps reveal strongly negative Pt4C16cores that likely facilitate ammonium cation binding. Analogous electronic properties of Pt3C12and Pt5C20homologs and selected equilibria are explored computationally.