3 years ago

Reactions of (Cyclopentadienylidenehydrazono)triphenylphosphorane with Chlororuthenium(II) Complexes and Substituent Effect on the Thermodynamic Trend in the Migratory-Insertion Reactions of Chlororuthenium–Alkylidene Complexes

Reactions of (Cyclopentadienylidenehydrazono)triphenylphosphorane with Chlororuthenium(II) Complexes and Substituent Effect on the Thermodynamic Trend in the Migratory-Insertion Reactions of Chlororuthenium–Alkylidene Complexes
Guochen Jia, Wei Bai, Ka-Ho Lee, Herman H. Y. Sung, Zhenyang Lin, Jiangxi Chen, Ian D. Williams
Reactions of (cyclopentadienylidenehydrazono)triphenylphosphorane with RuCl2(PPh3)3 or (η6-cymene)RuCl2(PPh3) in toluene produced the chlorocyclopentadienyl complex (η5-C5H4Cl)RuCl(PPh3)2, which was likely formed through the cyclopentadienylidene intermediate RuCl2{═C(C4H4)}(PPh3)2. Treatment of (η6-cymene)RuCl2(PPh3) with (cyclopentadienylidenehydrazono)triphenylphosphorane in methanol gave [(η5-C5H4Cl)Ru(η6-cymene)]+. Computational studies reveal that the thermodynamic stability of the analogous chlororuthenium complexes RuCl2(═CRR′)(PPh3)2 and [RuCl(═CRR′)(PMe3)(η6-C6H6)]+, with respect to the formation of the corresponding η5-chloropentadienyl complexes via a migratory carbene-insertion reaction is in the order of cyclopentadienylidene < indenylidene < fluorenylidene < phenylcarbene.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00427

DOI: 10.1021/acs.organomet.7b00427

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