title: Tuning the reactivity of dioxoruthenium(VI) porphyrins toward an arylimine by altering porphyrin substituents.
abstract: Reaction of dioxoruthenium(VI) porphyrins [Ru(VI)(Por)O2] with arylimine HN=CPh2 in dichloromethane afforded bis(methyleneamido)ruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)2] for Por = 4-Cl-TPP and TMP; (methyleneamido)hydroxoruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)(OH)] for Por = TPP and TTP; and bis(arylimine)ruthenium(II) porphyrins [Ru(II)(Por)(HN=CPh2)2] for Por = 3,5-Cl2TPP and 3,5-(CF3)2TPP. In dichloromethane solution exposed to air, complex [Ru(II)(3,5-Cl2TPP)(HN=CPh2)2] underwent oxidative deprotonation to form [Ru(IV)(3,5-Cl2TPP)(N=CPh2)2]. The new ruthenium porphyrins were identified by 1H NMR, UV-vis, IR, and mass spectroscopy, along with elemental analysis. X-ray crystal structure determinations of [Ru(IV)(4-Cl-TPP)(N=CPh2)2], [Ru(IV)(TPP)(N=CPh2)(OH)], and [Ru(II)(3,5-(CF3)2TPP)(HN=CPh2)2] revealed the Ru-N(methyleneamido) or Ru-N(arylimine) distances of 1.897(5) A (average), 1.808(4) A, and 2.044(2) A (average), respectively.
authors.affiliation: Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong. jshuang@hku.hk
authors.forename: Jie-Sheng
authors.initials: JS
authors.lastname: Huang
authors.forename: Sarana Ka-Yan
authors.initials: SK
authors.lastname: Leung
authors.forename: Zhong-Yuan
authors.initials: ZY
authors.lastname: Zhou
authors.forename: Nianyong
authors.initials: N
authors.lastname: Zhu
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che