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Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles
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https://doi.org/10.1021/acs.organomet.9b00633Abstract
Pyridine-terminated molecular rods and either (i) the cis-(dppp)(I)Pt(CC-triptycene-CC)Pt(I)(dppp) rod or (ii) the trans-(PEt3)2(I)Pt(CC-biphenyl-CC)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 (CC)Pt(PEt3)2(CC) components, in agreement with density functional theory calculations.
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