Research output: Contribution to journal › Article › peer-review
Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV). / Fedorenko, A. D.; Fomenko, I. S.; Gongola, M. I. et al.
In: Journal of Structural Chemistry, Vol. 62, No. 10, 10.2021, p. 1531-1542.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV)
AU - Fedorenko, A. D.
AU - Fomenko, I. S.
AU - Gongola, M. I.
AU - Pervukhina, N. V.
AU - Kalinkin, A. V.
AU - Nikolenko, A. D.
AU - Gushchin, A. L.
N1 - Publisher Copyright: © 2021, Pleiades Publishing, Ltd.
PY - 2021/10
Y1 - 2021/10
N2 - The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) Å, b = 25.2962(4) Å, с = 32.5478(6) Å, V = 19112.8(6) Å3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.
AB - The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) Å, b = 25.2962(4) Å, с = 32.5478(6) Å, V = 19112.8(6) Å3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.
KW - electronic structure
KW - niobium
KW - rhodanide
KW - single crystal XRD
KW - sulfide clusters
KW - X-ray electron spectroscopy
KW - XANES
KW - XPS
UR - http://www.scopus.com/inward/record.url?scp=85119137113&partnerID=8YFLogxK
U2 - 10.1134/S0022476621100073
DO - 10.1134/S0022476621100073
M3 - Article
AN - SCOPUS:85119137113
VL - 62
SP - 1531
EP - 1542
JO - Journal of Structural Chemistry
JF - Journal of Structural Chemistry
SN - 0022-4766
IS - 10
ER -
ID: 34679259