New soluble monomeric polyselenide anions, [MQ(Se4)2]2- (M = Mo, W; Q = O, S, Se)

Wardle, Robert W. M.; Mahler, Charles H.; Chau, Chung Nin; Ibers, James A.

doi:10.1021/ic00289a010

Cited by 52 publications

(25 citation statements)

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“…The first absorption may be attributed to an intraligand transition, and the shoulder is from the charge transfer of ligand to metal [LMCT (S → Cu)] in accordance with a similar assignment in [VS 4 Cu 4 (R 2 NCS 2 ) n (PhS) 4 - n ] 3- (R 2 = Et, C 4 H 8 O; n = 0, 1, 2) 6a which is red-shifted compared to the free [MoSe 4 ] 2- anion (367 nm) . The lowest absorption band at about 555 nm is relatively weak and may be due to the electron transfer between MoSe 4 2- and metal Cu.…”

Section: Resultssupporting

confidence: 76%

Chemistry of the Tetraselenomolybdate Anion: Syntheses, Spectroscopic Results, and Structural Characterizations of Polynuclear Mo−Cu−Se Compounds Containing Thiolate Ligands

et al. 1997

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In the study on the reactivity of tetraselenomolybdate, a DMF solution of [Et4N]2[MoSe4] was found to react with 3 equiv of CuCl in the presence of NaS2CNR2 [R2 = Et2, C5H10, (PhCH2)2, Me2] to give a series of Mo−Cu−Se compounds, [Et4N]2[MoCu3Se4(R2NCS2)3] (R2 = Et2 (1a), C5H10 (1b), (PhCH2)2 (1c)) and [Et4N]2[MoCu4Se4(Me2NCS2)4] (2). Furthermore, the reaction of 2 or [Et4N]2[MoSe4(CuCN)2] with [Et4N]2[Cu(SPh)3] in DMF/MeCN afforded a polynuclear Mo−Cu−Se cluster compound, [Et4N]4[MoCu10Se4(PhS)12] (3). [Et4N]2[MoCu3Se4(Et2NCS2)3] (1a) crystallizes in the orthorhombic space group P212121 with cell dimensions a = 12.949(3) Å, b = 13.339(3) Å, c = 29.744(6) Å, V = 5137.6 Å3, and Z = 4. Full anisotropic refinements of the structure led to convergence with a value of R = 0.052 (R w = 0.055) for 453 variables and 6854 reflections (F > 4.0σ(F)). The [MoCu3Se4(Et2NCS2)3]2- anion in 1a comprises three Et2NCS2Cu fragments linked by a slightly distorted tetrahedral MoSe4 moiety. Compound 2 crystallizes in the orthorhombic space group Pbca with cell constants a = 14.600(3) Å, b = 18.765(4) Å, c = 37.781(8) Å, V = 10351 Å3, and Z = 8. Anisotropic refinements with 5328 reflections (F > 4.0σ(F)) and 460 parameters for all non-hydrogen atoms yielded the values of R = 0.075 and R w = 0.080. The [MoCu4Se4(Me2NCS2)4]2- anion structure of 2, which possesses a pseudo D 2 d symmetry of the MoSe4Cu4 core and a nearly planar MoCu4 array, consists of four Me2NCS2Cu fragments coordinated across four edges of the tetrahedral [MoSe4]2- moiety. The compound [Et4N]4[MoCu10Se4(PhS)12] (3) crystallizes in the tetragonal space group I4̄ with cell dimensions a = 18.344(3) Å, c = 18.368(4) Å, V = 6180.9 Å3, and Z = 2. A value of R = 0.079 (R w = 0.084) for 218 parameters and 3314 observations (F > 4.0σ(F)) was obtained from anisotropic refinements of the non-hydrogen atoms. The [MoCu10Se4(PhS)12]4- anion structure of 3 can be described as six Cu atoms bonded across the six edges of a central MoSe4 tetrahedron, forming an octahedral MoSe4Cu6 array, to which the other four Cu atoms are added in a tetrahedral array bridged by 12 μ-SPh ligands. The 95Mo NMR spectra of the all compounds in DMF show a single resonance peak. Their chemical shifts are dependent on the deshielding effect from the number of the Cu atoms around Mo atom and the structures of the compounds. The 1H NMR, IR, and electronic spectroscopic data of these compounds are also consistent with their solid-state structures.

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Section: Resultssupporting

confidence: 76%

Chemistry of the Tetraselenomolybdate Anion: Syntheses, Spectroscopic Results, and Structural Characterizations of Polynuclear Mo−Cu−Se Compounds Containing Thiolate Ligands

et al. 1997

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“…The spectroscopy of the W2Se62-ion is fully compatible with the X-ray structure. Thus, the 77Se NMR resonance at 1559 ppm is well within the range expected for a terminal Se atom bound to a W center while the resonance at 591 ppm is near the range of 1000-600 ppm expected for "W-bound" Se atoms.3,6,7 The observation of W-Se coupling (J = 99 Hz) is consistent with this resonance being from a bridging Se atom. Although the oligomeric W/Se anions show no characteristic UV-vis bands, the W2Se62ĩ on does.…”

Section: Resultssupporting

confidence: 63%

Synthesis and characterization of bis[tetraphenylphosphonium] hexaselenoxoditungstate(2-)

Lü¹,

Ansari²,

Ibers³

1989

Inorg. Chem.

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“…In the framework of 1 , each T2 cluster ([In 4 Se 10 ] 8– ) is connected to other three T2 clusters via corner-sharing mode and the fourth corner is bonded to triangularly shaped μ 3 -Se 4 2– or μ 3 -T1 bridge (Figure a). The existence of μ 3 -Se 4 2– in compound 1 is further proven by Raman spectra (Figure S6), in which the wide band in the range of 262–277 cm –1 could be attributed to the Se–Se bonds of μ 3 -Se 4 2– . , The bond lengths of Se–Se (2.43 Å) in μ 3 -Se 4 2– and In–Se (2.66 Å) in μ 3 -T1 are acceptable, which are coincident with the reported values. − The ratio of μ 3 -Se 4 2– and μ 3 -T1, located at the same position (Figure S7), is about 1.25:1, which was obtained by structural refinement and further confirmed by EDS and EA analysis.…”

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confidence: 76%

Supertetrahedral Cluster-Based In–Se Open Frameworks with Unique Polyselenide Ion as Linker

Xue

Lin

Yang

et al. 2018

Crystal Growth & Design

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Reported here are three new In–Se open frameworks with unique polyselenide ion as linker. Single-crystal X-ray diffraction analyses demonstrate that supertetrahedral Tn (n = 2, 3) clusters serving as secondary building units in these compounds are connected via polyselenide ligands to form the interrupted or elongated diamond topologies. UV–vis absorption analysis and photoelectric response measurements indicate that these In–Se frameworks retain semiconductor properties, making them potential candidates in photocatalytic applications.

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New soluble monomeric polyselenide anions, [MQ(Se4)2]2- (M = Mo, W; Q = O, S, Se)

Abstract: A new synthetic route to tetraselenometalates MSe42‐ is exemplified in the scheme.

Cited by 52 publications

References 4 publications

Chemistry of the Tetraselenomolybdate Anion: Syntheses, Spectroscopic Results, and Structural Characterizations of Polynuclear Mo−Cu−Se Compounds Containing Thiolate Ligands

Chemistry of the Tetraselenomolybdate Anion: Syntheses, Spectroscopic Results, and Structural Characterizations of Polynuclear Mo−Cu−Se Compounds Containing Thiolate Ligands

Synthesis and characterization of bis[tetraphenylphosphonium] hexaselenoxoditungstate(2-)

Supertetrahedral Cluster-Based In–Se Open Frameworks with Unique Polyselenide Ion as Linker

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