Alkoxide ligand controlled self-assembling of (imido)vanadium(V) compounds having a tetrahedral VO3N geometry

• Published in: Journal of inorganic biochemistry Vol. 203; p. 110880
• Main Authors: Moriuchi, Toshiyuki, Sakuramoto, Takashi, Nishina, Masafumi, Donaka, Yosuke, Hirao, Toshikazu
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.02.2020
• Subjects: (Imido)vanadium(V) compound; C-H···O interaction; Crystal structure; Metal-nitrogen multiple; Self-assembling; Tetrahedral coordination geometry; (Imido)vanadium(V) compound; C-H···O interaction; Self-assembling; Tetrahedral coordination geometry; Metal-nitrogen multiple; Crystal structure
• ISSN: 0162-0134; 1873-3344
• DOI: 10.1016/j.jinorgbio.2019.110880

The reaction of (1S,2S)-(−)-1,2-diphenylethylenediamine with VO(OiPr)3 in the presence of NaH was found to afford the binuclear (imido)vanadium(V) triisopropoxide, [(OiPr)3V(N-meso-1,2-DPE-N)V(OiPr)3] (DPE = diphenylethylene), (1aRS/SS). Using (1R,2R)-(+)-1,2-diphenylethylenediamine as a starting material, one-step reaction also proceeded to form the binuclear (imido)vanadium(V) triisopropoxide, [(OiPr)3V(N-meso-1,2-DPE-N)V(OiPr)3], (1aRS/RR). The single-crystal X-ray structure determination of 1aRS/SS revealed the hydrogen-bonded self-assembled structure utilizing the advantage of anti-conformation through the intermolecular hydrogen bonds of C-H···O pattern between phenyl and isopropoxide moieties, wherein each vanadium atom is coordinated in a nearly tetrahedral VO3N geometry (τ4 = 0.017 and 0.057). On the contrary, a discrete (imido)vanadium(V) tris(triphenylsiloxide) unit, which possesses a nearly tetrahedral VO3N arrangement around the vanadium metal center (τ4 = 0.060), was observed in the crystal structure of the (4-methoxyphenylimido)vanadium(V) tris(triphenylsiloxide), [(p-MeOC6H4N)V(OSiPh3)3], (1b) with bulky triphenylsiloxide ligands. The binuclear (imido)vanadium(V) triisopropoxide having a tetrahedral VO3N geometry was obtained by using one-step synthesis, leading to the formation of the hydrogen-bonded self-assembled structure through the intermolecular hydrogen bonds of CH • • • O pattern. [Display omitted] •One-step synthesis of the binuclear (imido)vanadium(V) triisopropoxide was performed.•A tetrahedral coordination geometry was observed in the vanadium atom center.•The C-H···O intermolecular hydrogen bonding network was formed.•The (imido)vanadium(V) tris(triphenylsiloxide) compound was present independently.