Facile Substitution of Bridging SO22– Ligands in Re12 Bioctahedral Cluster Complexes
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Inorganic Chemistry
ISSN: 0020-1669
, E-ISSN: 1520-510X
|
| Output data |
Year: 2017,
Volume: 56,
Number: 20,
Pages: 12389-12400
Pages count
: 12
DOI:
10.1021/acs.inorgchem.7b01889
|
| Tags |
ORDER REGULAR APPROXIMATION; RHENIUM CLUSTER; STRUCTURAL-CHARACTERIZATION; SOLUTION CHEMISTRY; SCREENING MODEL; SULFUR-DIOXIDE; CORE; SOLVATION; EXCHANGE; ENVIRONMENT |
| Authors |
Gayfulin Yakov M.
1
,
Smolentsev Anton I.
1,2
,
Kozlova Svetlana G.
1,2
,
Novozhilov Igor N.
1
,
Plyusnin Pavel E.
1,2
,
Kompankov Nikolay B.
1,2
,
Mironov Yuri V.
1,2
|
| Affiliations |
| 1 |
Nikolaev Institute of Inorganic Chemistry SB RAS
|
| 2 |
Novosibirsk State University
|
|
Selective substitution of μ-SO22– groups by either O2– or Se2– ions occurs upon heating the bioctahedral rhenium cluster complex K6[Re12CS14(μ-SO2)3(CN)6] in air atmosphere or in the presence of a Se source, respectively, manifesting the remarkable lability of SO22– ligands bound to a transition-metal cluster. A series of compounds based on the new mixed-ligand anions, [Re12CS14(μ-O)3(CN)6]6–, [Re12CS14(μ-Se)3(CN)6]6–, and [Re12CS14(μ-O)3(OH)6]6–, were isolated and their solid-state structures were elucidated by single-crystal X-ray diffraction analysis. Along with the previously reported μ-sulfide clusters, the new species constitute a series of rhenium anionic complexes with the common formula [Re12CS14(μ-Q)3L6]6– (Q = O, S, Se, L = CN–; Q = O, S, L = OH–), within which the total charge and number of cluster valence electrons (CVEs) are constant. The article presents insights into the mechanistic and synthetic aspects of the substitution process, and it comprehensively discusses the influence of inner ligand environment on the structure, spectroscopic characteristics, and electrochemical behavior of the novel compounds.