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[Ni^III(OMe)]-mediated reductive activation of CO₂ affording a Ni(κ¹-OCO) complex.

ABSTRACT: Carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C₁ sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO₂, i.e. insertion of CO₂ producing bicarbonate/acetate/formate, cleavage of CO₂ yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO₂ affording CO/HCOOH/CH₃OH/CH₄/C₂H₄/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO₂ by the [Ni^III(OMe)(P(C₆H₃-3-SiMe₃-2-S)₃)]^- complex, yielding the [Ni^III(κ¹-OCO˙^-)(P(C₆H₃-3-SiMe₃-2-S)₃)]^- complex. The formation of this unusual Ni^III(κ¹-OCO˙^-) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [Ni^III(SPh)], [Ni^II(CO)], and [Ni^II(N₂H₄)] toward CO₂, in contrast, demonstrates that the ionic [Ni^III(OMe)] core attracts the binding of weak σ-donor CO₂ and triggers the subsequent reduction of CO₂ by the nucleophilic [OMe]^- in the immediate vicinity. This metal-ligand cooperative activation of CO₂ may open a novel pathway promoting the subsequent incorporation of CO₂ in the buildup of functionalized products.

SUBMITTER: Chiou TW

PROVIDER: S-EPMC6008733 | biostudies-literature | 2016 Jun

REPOSITORIES: biostudies-literature

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[NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex.

Chiou Tzung-Wen TW Tseng Yen-Ming YM Lu Tsai-Te TT Weng Tsu-Chien TC Sokaras Dimosthenes D Ho Wei-Chieh WC Kuo Ting-Shen TS Jang Ling-Yun LY Lee Jyh-Fu JF Liaw Wen-Feng WF

Chemical science 20160224 6

Carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO2, i.e. insertion of CO2 producing bicarbonate/acetate/formate, cleavage of CO2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO2 affording CO/HCOOH/CH3OH/CH4/C2H4/ ...[more]

PMID: 30008996

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Project description:Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Dataset Information

[Ni^III(OMe)]-mediated reductive activation of CO₂ affording a Ni(κ¹-OCO) complex.

Publications

[Ni<sup>III</sup>(OMe)]-mediated reductive activation of CO<sub>2</sub> affording a Ni(κ<sup>1</sup>-OCO) complex.

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