Stabilization of Re-3(7+)/Re-3(8+) Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)(9)](4-)/[{Re3X3}(CN)(9)](5-) (X = Br or I)

Standard

Stabilization of Re-3(7+)/Re-3(8+) Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)(9)](4-)/[{Re3X3}(CN)(9)](5-) (X = Br or I). / Yarovoy, Spartak S.; Gayfulin, Yakov M.; Smolentsev, Anton и др.

в: Inorganic Chemistry, Том 60, № 8, 19.04.2021, стр. 5980-5987.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{f5ca194ef44346a6ab892cc25cf2c6ec,

title = "Stabilization of Re-3(7+)/Re-3(8+) Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)(9)](4-)/[{Re3X3}(CN)(9)](5-) (X = Br or I)",

abstract = "The interaction of rhenium(III) halides Re3Br9 and Re3I9 with aqueous solution of sodium cyanide resulted in the formation of the first trinuclear halide-cyanide rhenium cluster complexes [{Re3X3}(CN)9]5-/[{Re3X3}(CN)9]4- (X = Br or I) crystallized as salts of the compositions Cs4Na[{Re3Br3}(CN)9]·5.25H2O (1), Cs4Na[{Re3I3}(CN)9]·6H2O (2), Cs4[{Re3Br3}(CN)9]·2H2O·0.5CsCl (3), and Cs4[{Re3I3}(CN)9]·(4). All of the compounds are stable in air in the solid state and in aqueous solution. The substitution of apical halide ligands in the parent compounds Re3X9 by cyanides led to reduction of the original metallocluster Re39+ (12 cluster valence electrons (CVEs)) to Re37+ (14 CVEs), forming the compounds 1 and 2. The apical CN- ligands affect the electronic structure of the Re3 metallocluster stabilizing reduced form. Complexes 1 and 2 represent the first examples of triangular rhenium clusters with the Re37+ metallocluster. The reaction of 1 and 2 with H2O2 resulted in formation of compounds 3 and 4 with the formal charge of the Re3 metallocluster equal to 8+, and no further oxidation to Re39+ occurred. The compounds were characterized by the X-ray diffraction analysis, NMR and UV-vis spectroscopies, mass spectrometry, cyclic voltammetry, and magnetic susceptibility measurements.",

keywords = "CRYSTAL-STRUCTURE, MOLECULAR-STRUCTURE, COORDINATION, REDUCTION, CHEMISTRY, PRODUCTS, RE3CL9, YIELD",

author = "Yarovoy, {Spartak S.} and Gayfulin, {Yakov M.} and Anton Smolentsev and Yanshole, {Vadim V.} and Yuri Mironov",

year = "2021",

month = apr,

day = "19",

doi = "10.1021/acs.inorgchem.1c00399",

language = "English",

volume = "60",

pages = "5980--5987",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

}

RIS

TY - JOUR

T1 - Stabilization of Re-3(7+)/Re-3(8+) Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)(9)](4-)/[{Re3X3}(CN)(9)](5-) (X = Br or I)

AU - Yarovoy, Spartak S.

AU - Gayfulin, Yakov M.

AU - Smolentsev, Anton

AU - Yanshole, Vadim V.

AU - Mironov, Yuri

PY - 2021/4/19

Y1 - 2021/4/19

N2 - The interaction of rhenium(III) halides Re3Br9 and Re3I9 with aqueous solution of sodium cyanide resulted in the formation of the first trinuclear halide-cyanide rhenium cluster complexes [{Re3X3}(CN)9]5-/[{Re3X3}(CN)9]4- (X = Br or I) crystallized as salts of the compositions Cs4Na[{Re3Br3}(CN)9]·5.25H2O (1), Cs4Na[{Re3I3}(CN)9]·6H2O (2), Cs4[{Re3Br3}(CN)9]·2H2O·0.5CsCl (3), and Cs4[{Re3I3}(CN)9]·(4). All of the compounds are stable in air in the solid state and in aqueous solution. The substitution of apical halide ligands in the parent compounds Re3X9 by cyanides led to reduction of the original metallocluster Re39+ (12 cluster valence electrons (CVEs)) to Re37+ (14 CVEs), forming the compounds 1 and 2. The apical CN- ligands affect the electronic structure of the Re3 metallocluster stabilizing reduced form. Complexes 1 and 2 represent the first examples of triangular rhenium clusters with the Re37+ metallocluster. The reaction of 1 and 2 with H2O2 resulted in formation of compounds 3 and 4 with the formal charge of the Re3 metallocluster equal to 8+, and no further oxidation to Re39+ occurred. The compounds were characterized by the X-ray diffraction analysis, NMR and UV-vis spectroscopies, mass spectrometry, cyclic voltammetry, and magnetic susceptibility measurements.

AB - The interaction of rhenium(III) halides Re3Br9 and Re3I9 with aqueous solution of sodium cyanide resulted in the formation of the first trinuclear halide-cyanide rhenium cluster complexes [{Re3X3}(CN)9]5-/[{Re3X3}(CN)9]4- (X = Br or I) crystallized as salts of the compositions Cs4Na[{Re3Br3}(CN)9]·5.25H2O (1), Cs4Na[{Re3I3}(CN)9]·6H2O (2), Cs4[{Re3Br3}(CN)9]·2H2O·0.5CsCl (3), and Cs4[{Re3I3}(CN)9]·(4). All of the compounds are stable in air in the solid state and in aqueous solution. The substitution of apical halide ligands in the parent compounds Re3X9 by cyanides led to reduction of the original metallocluster Re39+ (12 cluster valence electrons (CVEs)) to Re37+ (14 CVEs), forming the compounds 1 and 2. The apical CN- ligands affect the electronic structure of the Re3 metallocluster stabilizing reduced form. Complexes 1 and 2 represent the first examples of triangular rhenium clusters with the Re37+ metallocluster. The reaction of 1 and 2 with H2O2 resulted in formation of compounds 3 and 4 with the formal charge of the Re3 metallocluster equal to 8+, and no further oxidation to Re39+ occurred. The compounds were characterized by the X-ray diffraction analysis, NMR and UV-vis spectroscopies, mass spectrometry, cyclic voltammetry, and magnetic susceptibility measurements.

KW - CRYSTAL-STRUCTURE

KW - MOLECULAR-STRUCTURE

KW - COORDINATION

KW - REDUCTION

KW - CHEMISTRY

KW - PRODUCTS

KW - RE3CL9

KW - YIELD

UR - http://www.scopus.com/inward/record.url?scp=85105093236&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.1c00399

DO - 10.1021/acs.inorgchem.1c00399

M3 - Article

C2 - 33821642

VL - 60

SP - 5980

EP - 5987

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -

ID: 28761592