Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles

Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles
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机械应变与电子应变:椭圆形炔基-Pt(II)-膦大环化合物

DOI:
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发表时间:
2019
期刊:
影响因子:
2.8
通讯作者:
J. Michl
J. Michl
中科院分区:
化学2区
文献类型:
--
作者:
Jan Plutnar;Cécile Givelet;C. Lemouchi;Jana Jaklová Dytrtová;I. Císařová;S. Teat;J. Michl

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吡啶封端的分子棒和 (i) 顺式-(dppp)(I)Pt(C=C-三蝶烯-C=C)Pt(I)(dppp) 棒或 (ii) 反式-(PEt3)2(I)Pt(C=C-联苯-C=C)Pt(I)(PEt3)2 棒组装成大环,通过 NMR、ESI-IMS 进行表征,并且在两种情况下还单晶X射线衍射。前者形成具有含双齿膦顺式配位 Pt(II)-炔角的矩形。在后者中,Pt中心对反式构型的偏好推翻了三键对线性的偏好,NMR表明它们具有椭圆形结构,具有交替的弯曲杆和弯曲反式(C=C)Pt(PEt3)2(C=C)组分,这与密度泛函理论计算一致。
Pyridine-terminated molecular rods and either (i) the cis-(dppp)(I)Pt(C≡C-triptycene-C≡C)Pt(I)(dppp) rod or (ii) the trans-(PEt3)2(I)Pt(C≡C-biphenyl-C≡C)Pt(I)(PEt3)2 rod assemble into macrocycles, characterized by NMR, ESI-IMS, and in two cases also single-crystal X-ray diffraction. The former form rectangles with bidentate phosphine-containing cis-coordinated Pt(II)-alkyne corners. In the latter, the preference of the Pt centers for a trans configuration overrules the preference of the triple bonds for linearity and NMR shows that they have oval structures with alternating bent rod and bent trans (C≡C)Pt(PEt3)2(C≡C) components, in agreement with density functional theory calculations.
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