TY - JOUR

T1 - The (Dioximate)NiII/I2 System

T2 - Ligand Oxidation and Binding Modes of Triiodide Species

AU - Efimenko, Zarina M.

AU - Novikov, Alexander S.

AU - Ivanov, Daniil M.

AU - Piskunov, Alexandr V.

AU - Vereshchagin, Anatoly A.

AU - Levin, Oleg V.

AU - Bokach, Nadezhda A.

AU - Kukushkin, Vadim Yu.

PY - 2020/2/17

Y1 - 2020/2/17

N2 - Reinvestigation of (o-benzoquinonedioximate)2Ni/I2 systems demonstrated that the reaction itself and also the crystallization conditions dramatically affect the identity of generated species. Crystallization (CHCl3, 20-25 °C) of the nickel(II) dioximate complex [Ni(bqoxH)2] (bqoxH2 = o-benzoquinonedioxime) with I2 in the 1:(1-10) molar ratios of the reactants led to several (o-benzoquinonedioximate)2Ni derivatives and/or iodine adducts [Ni(I)(bqoxH)(bqoxH2)]·3/2I2, [Ni(I3)(bqoxH)(bqoxH2)]·[Ni(bqoxH)2], and [Ni(I3)(bqox•-)(bqoxH2)]·I2; the latter one, featuring the anion-radical bqox•- ligand, is derived from the formal (-2H+/1e-)-oxidation of bqoxH2. In these three adducts, various types of noncovalent interactions were identified experimentally and their existence was supported theoretically. The [Ni(I3)(bqox•-)(bqoxH2)]·I2 adduct exhibits simultaneous semicoordination and coordination patterns of the triiodide ligand; this is the first recognition of the semicoordination of any polyiodide ligand to a metal center. The semicoordination noncovalent contact Ni···I3 (3.7011(10) Å) is substantially longer that the Ni-I3 coordination bond (2.8476(9) Å), and the difference in energies between these two types of linkages is 8-12 kcal/mol.

AB - Reinvestigation of (o-benzoquinonedioximate)2Ni/I2 systems demonstrated that the reaction itself and also the crystallization conditions dramatically affect the identity of generated species. Crystallization (CHCl3, 20-25 °C) of the nickel(II) dioximate complex [Ni(bqoxH)2] (bqoxH2 = o-benzoquinonedioxime) with I2 in the 1:(1-10) molar ratios of the reactants led to several (o-benzoquinonedioximate)2Ni derivatives and/or iodine adducts [Ni(I)(bqoxH)(bqoxH2)]·3/2I2, [Ni(I3)(bqoxH)(bqoxH2)]·[Ni(bqoxH)2], and [Ni(I3)(bqox•-)(bqoxH2)]·I2; the latter one, featuring the anion-radical bqox•- ligand, is derived from the formal (-2H+/1e-)-oxidation of bqoxH2. In these three adducts, various types of noncovalent interactions were identified experimentally and their existence was supported theoretically. The [Ni(I3)(bqox•-)(bqoxH2)]·I2 adduct exhibits simultaneous semicoordination and coordination patterns of the triiodide ligand; this is the first recognition of the semicoordination of any polyiodide ligand to a metal center. The semicoordination noncovalent contact Ni···I3 (3.7011(10) Å) is substantially longer that the Ni-I3 coordination bond (2.8476(9) Å), and the difference in energies between these two types of linkages is 8-12 kcal/mol.

KW - MIXED-VALENCE SOLIDS

KW - ZETA BASIS-SETS

KW - NONCOVALENT INTERACTIONS

KW - COORDINATION CHEMISTRY

KW - COPPER(II) COMPOUNDS

KW - MOLECULAR-STRUCTURE

KW - RATIONAL SYNTHESIS

KW - CRYSTAL-STRUCTURE

KW - X-RAY

KW - METAL

UR - http://www.scopus.com/inward/record.url?scp=85079563003&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/68b6c66c-9e0d-39fe-8b70-4eba1128a4a6/

U2 - 10.1021/acs.inorgchem.9b03132

DO - 10.1021/acs.inorgchem.9b03132

M3 - Article

C2 - 32027131

AN - SCOPUS:85079563003

VL - 59

SP - 2316

EP - 2327

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -