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Ruthenium Vinylidene Complexes Generated by Selective 1,2-Migration of P- and S-Substituents: Synthesis, Structures, and Dichromism Arising from an Intramolecular CH···O Hydrogen Bond
Organometallics ( IF 3.804 ) Pub Date : 2020-02-19 , DOI: 10.1021/acs.organomet.9b00856
Takuya Kuwabara; Yutaka Aoki; Kousuke Sakajiri; Kazuki Deguchi; Shuhei Takamori; Ai Hamano; Keiko Takano; Hirohiko Houjou; Youichi Ishii

Investigation of the vinylidene rearrangement of phosphorus- and sulfur-substituted internal alkynes at a ruthenium center unveiled selective 1,2-migration of P- and S-substituents and unexpected dichromatic behaviors of a part of the resulting vinylidene complexes. Reactions of [CpRu(dppe)Cl] and R1C≡CR2, where R1 = alkyl, Ar and R2 = P(═O)(OR)2, P(═O)R2, SR, SO2R, in the presence of NaBArF4 afforded the corresponding vinylidene complexes [CpRu{═C═C(R1)(R2)}(dppe)][BArF4], which were fully characterized by NMR and elemental analysis and, in some cases, X-ray diffraction analysis. 13C-labeling experiments disclosed selective migration of the P- and S-substituents. To our surprise, some of the products displayed dichromatic characters: although solutions of all the vinylidene products are yellow, several products were obtained as yellow and red crystals, others as red-purple crystals, and the rest as yellow crystals. UV–vis absorption spectra for the complexes displaying a dichromatic nature were recorded both in solution and in the solid state. X-ray diffraction analysis revealed that an intramolecular CH···O hydrogen bond between one of the methylene CH bonds in the dppe ligand and the E═O group (E = P, S) is present in the red and the red-purple crystals, which affects the conformation of the vinylidene ligand. In contrast, such hydrogen bonds were not observed in the yellow crystals. Time-dependent density functional theory (TD-DFT) analysis based on the crystal structures revealed that the structural changes of the vinylidene ligand upon the hydrogen bonding account for the dichromism.
更新日期:2020-02-19

 

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