Co(I) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal-ligand cooperation platform.

Dalton Trans

Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8577, Japan. and Interdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.

Published: October 2020

AI Article Synopsis

  • A series of cobalt(i) complexes with a unique tetradentate ligand named PNNP were synthesized and analyzed, including [CoCl(PNNP)], [CoMe(PNNP)], and [Co(CH2SiMe3)(PNNP)].
  • Upon heating, complex [Co(CH2SiMe3)(PNNP)] underwent structural changes to become [Co(PNNP')], featuring a modified ligand structure.
  • The transformation process was linked to the breaking of specific bonds, and complex [Co(PNNP'')] was able to cleave hydrogen gas into its structure at room temperature.

Article Abstract

A series of low spin cobalt(i) complexes bearing a tetradentate phenanthroline-based PNNP ligand (2,9-bis((diphenylphosphanyl)methyl)-1,10-phenanthroline), [CoCl(PNNP)] (1), [CoMe(PNNP)] (2) and [Co(CH2SiMe3)(PNNP)] (3), were synthesized and structurally identified. Complex 3 underwent a structural rearrangement of the PNNP skeleton upon heating to form [Co(PNNP')] (4), which is supported by an asymmetrical PNNP' ligand with a dearomatized phenanthroline backbone. Mechanistic studies supported that the transformation from 3 to 4 was initiated by the homolysis of either a Co-CH2SiMe3 bond or a benzylic C-H bond. Complex 4 achieved H-H bond cleavage of H2 (1 atm) at ambient temperature, to form [Co(PNNP'')] (6), in which two H atoms were incorporated into the endocyclic double bond of the PNNP'' ligand backbone.

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http://dx.doi.org/10.1039/d0dt02549fDOI Listing

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Co(I) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal-ligand cooperation platform.

Dalton Trans

October 2020

Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8577, Japan. and Interdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.

Article Synopsis
  • A series of cobalt(i) complexes with a unique tetradentate ligand named PNNP were synthesized and analyzed, including [CoCl(PNNP)], [CoMe(PNNP)], and [Co(CH2SiMe3)(PNNP)].
  • Upon heating, complex [Co(CH2SiMe3)(PNNP)] underwent structural changes to become [Co(PNNP')], featuring a modified ligand structure.
  • The transformation process was linked to the breaking of specific bonds, and complex [Co(PNNP'')] was able to cleave hydrogen gas into its structure at room temperature.
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