Synthetic, spectroscopic, x-ray structural, and quantum-chemical studies of cyanothiomolybdates with Mo2S2, Mo3S4 and Mo4S4 cores: a remarkable class of species existing with different electron populations and having the same central units as the ferredoxins

Müller, Achim; Jostes, Rainer; Eltzner, Werner; Nie, C.-S.; Diemann, E.; Bögge, Hartmut; Zimmermann, M.; Dartmann, M.; Reinsch‐Vogell, Uta; Che, S.; Cyvin, S. J.; Cyvin, B. N.

doi:10.1021/ic00213a002

Cited by 105 publications

(39 citation statements)

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“…The highest occupied MO (HOMO) and LUMO in [M] + are predominantly composed of Mo 4d atomic orbitals (AOs; 53 and 46 %, respectively). This picture is qualitatively consistent with the classical bonding scheme in M 3 Q 4 clusters, in which the HOMO (1e orbital in the C 3 v group) is responsible for the M–M bonding, and the LUMO (2a 1 orbital in the C 3 v group) is also metal‐centered and weakly bonding (with respect to the M–M bond) 17…”

Section: Resultssupporting

confidence: 86%

Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

et al. 2014

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Section: Resultssupporting

confidence: 86%

Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

et al. 2014

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“…The X-ray powder diffraction data of (2) synthesized by adopting the alternative route are almost matching to that reported in literature 20 . The similarities between the model substances for the ferredoxins and the complexes under study regarding their formal electron-transfer properties are striking.…”

Section: Synthesis Of K 8 [Mo 4 S 4 (Cn) 12 ]•4h 2 O Methods A: Conversupporting

confidence: 85%

“…The tetramer complex ion [Mo 4 S 4 (CN) 12 ] 8was obtained as a by-product of the reaction in the very low yield (Can 1.25 % based on starting material). The high yield of 1 and very low yield of 2 suggest that the trinuclear cluster units are already present in the amophous MoS 3 a part of which gets slowly convert to the tetramer unit 2 under the available reducing atmosphere of KCN 20 . The phenomenon of this core conversion has also been confirmed experimentally by the another that on reducing the aqueous solution of 1 with KOH and Al-powder it generates 2 in near quantitative yield.…”

Section: Synthesis Of K 8 [Mo 4 S 4 (Cn) 12 ]•4h 2 O Methods A: Convermentioning

confidence: 99%

Electrochemical Generation of Cyano Ligated Molybdenum Sulphur Tetramer Cubane Core: Synthesis and Characterization

Anamika¹,

Sah²,

Kumar³

2013

Asian J. Chem.

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For the first time the conversion of trimeric {M3S4} 4+ to tetrameric (M4S4} 4+ core has been made for molybdenum complex. The complex, K5[Mo3S4(CN)9] (1) on using with strong reducing agent transformed into K8[Mo4S4(CN)12] (2) in near quantitative yield. The diamagnetic complex (1) containing {Mo3} 6 core can accommodate two electrons in its non bonding molecular orbital 2a1 under reducing environment to give a complex ion [Mo3S4(CN)9] 7with [Mo3] 8 electronic configuration. This reduced species undergoes re-oxidation by atmospheric air to give back the original compound with [Mo3] 6 core via a partially oxidized an intermediate species [Mo3S4(CN)9] 6with [Mo3] 7 core shows a characteristic EPR signal. However, under drastic reducing condition, the two electrons reduced species [Mo3S4(CN)9] 7with [Mo3] 8 core accommodate the next coming electron to its antibonding 2e orbital and thus achieve an unstable tri-nuclear [Mo3(III)] 9 core, where each metal centre has been reduced by one electron. The highly unstable and super reduced species [Mo3S4(CN)9] 8with [Mo3(III)] 9 configuration undergoes core transformation from cuboidal trinuclear [Mo3(IV)S4] 4+ to the cubane type tetranuclear core [Mo4(III)S4] 4+ of [Mo4S4(CN)12] 8complex ion. The corresponding tungsten-analogue though responses this reduction, but quickly oxidizes back to the starting material during work-up procedure.

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“…The proposed arrangement of MoS3 corresponds to a formal charge state of MO"(S~~-)I,~(S")~. However, recent literature (7,8) and results reported here, indicate that this structure, which is based on that of thectystulline trichaicogenides of the group IVB and VB elements, is unlikely to be valid for MoS3.…”

mentioning

confidence: 58%

The Structure of Amorphous MoS₃

Weber

Muijsers

Niemantsverdriet

1995

Bulletin des Soc Chimique

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The compound MOSS has often been invoked as an intermediate in the surdation of molybdenum-based hydrodesulfurization catalysts (1 -4). According to Liang et al. (5,6), MoS3 has a chain-like arrangement of molybdenum atoms, which have a trigonal prismatic coordination of six sulfur atoms. Adjacent molybdenum atoms are bridged by three sulfur atoms along the chain. Every two metal atoms in the chain are paired up with a shorter metal-metal distance and one S-S bond in every other triangle. The proposed arrangement of MoS3 corresponds to a formal charge state of MO"(S~~-)I,~(S")~. However, recent literature (7,8) and results reported here, indicate that this structure, which is based on that of thectystulline trichaicogenides of the group IVB and VB elements, is unlikely to be valid for MoS3.In this contribution we report spectroscopic and chemical experiments aimed at elucidating the structure of MoS3 and the way it forms from (NH4)2MoS4. These compounds have been investigated with monochromatic X-ray photoemission (XPS), in situ Raman and infrared emission spectroscopy. XPS shows that all molybdenum in MoS3 occurs in the 4 + oxidation state, while sulfur is present in at least two states, including s2as well as ~2~-ligancis in different types of coordination. The emission infrared spectrum of MoS3 exhibits characteristic vibrations that are also encountered in the absorption infrared spectrum of the triangular (NH4)2[MmSi3]H20 cluster compound.Chemical extrusion experiments, aimed at identifying structural units inside MoS3, reveal that three triangular Mow-complexes, namely (NH4)2[Mo3Si3] H20, kIMo3S4(CN)s]2H20 and (NEt4)2[MosS7Cls] can be formed by treating MoS3 with reactions that are essentially destructive. Based on these results it is proposed that MoS3 is an aggregation of M0'~3-sulfur clusters.vely visualized in real time within the transmission electron microscope.

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Synthetic, spectroscopic, x-ray structural, and quantum-chemical studies of cyanothiomolybdates with Mo2S2, Mo3S4 and Mo4S4 cores: a remarkable class of species existing with different electron populations and having the same central units as the ferredoxins

Abstract: Spektroskopische (IR, RA, Elektronenabsorption, PE) Eigenschaften der Cyanothiomolybdate (I)‐(IV), die möglicherweise biologische Bedeutung haben, werden untersucht und auf der Grundlage von EH‐SCCC‐MO‐Berechnungen diskutiert.

Cited by 105 publications

References 4 publications

Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

Electrochemical Generation of Cyano Ligated Molybdenum Sulphur Tetramer Cubane Core: Synthesis and Characterization

The Structure of Amorphous MoS₃

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Synthetic, spectroscopic, x-ray structural, and quantum-chemical studies of cyanothiomolybdates with Mo2S2, Mo3S4 and Mo4S4 cores: a remarkable class of species existing with different electron populations and having the same central units as the ferredoxins

Abstract: Spektroskopische (IR, RA, Elektronenabsorption, PE) Eigenschaften der Cyanothiomolybdate (I)‐(IV), die möglicherweise biologische Bedeutung haben, werden untersucht und auf der Grundlage von EH‐SCCC‐MO‐Berechnungen diskutiert.

Cited by 105 publications

References 4 publications

Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior

Electrochemical Generation of Cyano Ligated Molybdenum Sulphur Tetramer Cubane Core: Synthesis and Characterization

The Structure of Amorphous MoS3

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The Structure of Amorphous MoS₃