TY - JOUR

T1 - First Pentanuclear Molybdenum Iodide Cluster (Bu4N)[Mo5OI13]: Synthesis and Structure

AU - Mikhaylov, M. A.

AU - Sukhikh, T. S.

AU - Sheven’, D. G.

AU - Sokolov, M. N.

N1 - Funding Information: This work was supported by state assignment of the Nikolaev Institute of Inorganic Chemistry (Siberian Branch, Russian Academy of Sciences) in the area of basic research. Publisher Copyright: © 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/8

Y1 - 2021/8

N2 - The first iodide cluster of molybdenum with the metal cage in the form of a tetragonal pyramid (Bu4N)[Mo5OI13]·THF (I) and cocrystallizate (Bu4N){[Mo5OI13]0.9[Mo6I14]·THF (II) are synthesized for the first time by heating a LiI–I2–Mo mixture in a temperature range of 300–400°С followed by the extraction of the product. Complexes I and II are studied by X-ray diffraction analysis (CIF files CCDC nos. 2063029 (I) and 2063030 (II)). The molybdenum atoms in [Mo5OI13]– form a square pyramid with Mo–Mo distances of 2.67 Å between the basal molybdenum atoms and the Mo–Mo distances equal to 2.72 Å between the apical and basal molybdenum atoms. The oxygen atom is coordinated to the pyramid base (Mo–μ4-O 2.10 Å). The cluster anion [Mo5OI13]– can be presented as the octahedral cluster anion [Mo6I14]2– in which the position of the {MoI}– fragment (d0, 6e) is occupied by the isoelectronic oxygen atom (s2p4, 6e). In the structure of compound II, the [Mo5OI13]– and [Mo6I14]2– cluster anions occupy close atomic positions.

AB - The first iodide cluster of molybdenum with the metal cage in the form of a tetragonal pyramid (Bu4N)[Mo5OI13]·THF (I) and cocrystallizate (Bu4N){[Mo5OI13]0.9[Mo6I14]·THF (II) are synthesized for the first time by heating a LiI–I2–Mo mixture in a temperature range of 300–400°С followed by the extraction of the product. Complexes I and II are studied by X-ray diffraction analysis (CIF files CCDC nos. 2063029 (I) and 2063030 (II)). The molybdenum atoms in [Mo5OI13]– form a square pyramid with Mo–Mo distances of 2.67 Å between the basal molybdenum atoms and the Mo–Mo distances equal to 2.72 Å between the apical and basal molybdenum atoms. The oxygen atom is coordinated to the pyramid base (Mo–μ4-O 2.10 Å). The cluster anion [Mo5OI13]– can be presented as the octahedral cluster anion [Mo6I14]2– in which the position of the {MoI}– fragment (d0, 6e) is occupied by the isoelectronic oxygen atom (s2p4, 6e). In the structure of compound II, the [Mo5OI13]– and [Mo6I14]2– cluster anions occupy close atomic positions.

KW - clusters

KW - crystal structure

KW - iodine

KW - molybdenum

KW - oxoiodides

KW - self-assembling

UR - http://www.scopus.com/inward/record.url?scp=85112466467&partnerID=8YFLogxK

U2 - 10.1134/S1070328421080030

DO - 10.1134/S1070328421080030

M3 - Article

AN - SCOPUS:85112466467

VL - 47

SP - 560

EP - 566

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 8

ER -