Exploring the Breadth of Terminal Ligands Coordinated in [Mo6X8]4+- and [Re6Q8]2+-Based Cluster Complexes

Szczepura, Lisa F.; Soto, Ernesto

doi:10.1007/430_2019_32

Cited by 8 publications

(5 citation statements)

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“…[28] Another fresh review in a related area covers some aspects of coordination chemistry of phosphorescent clusters with {Re 6 Q 8 } 2+ and {Mo 6 X 8 } 4+ cores (Q = S, Se, Te; X = Cl, Br, I), and gives food compementary material tot he latter chapets of this review. [29]…”

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confidence: 99%

Molybdenum Iodides – from Obscurity to Bright Luminescence

Mikhaylov

Sokolov

2019

Eur J Inorg Chem

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This review is dedicated to the chemistry of Mo iodides. These compounds have a humble origin, and for a long time their chemistry has been almost completely neglected. Although important work on mononuclear and dinuclear Mo iodide complexes was done in 1980-1990s, the situation has dramatically changed within the last decade. The finding that the IntroductionThe iodides of transition metals attract much less attention than their chloride and bromide analogues, even though a book dealing exclusively with metal iodides was published half a century ago. [1] This is partly explainable by general lack of current or proposed practical use for this class of compounds. A notable exception offer the volatile iodides of Ti, Zr, and Hf, and of a few other metals, that can be used in the iodide process of van Arkel and de Boer. [2] Among the group 6 metals, this process can be applied for preparation of high purity chromium, which [a] Nikolaev His research interests focus on the coordination chemistry of 4d and 5d transition metals. Maxim Mikhaylov was born in Novosibirsk, (Russia). In 2009-2013 he completed his Ph. D. at the Laboratory of cluster and supramolecular compounds in the Nikolaev Institute of Inorganic Chemistry (NIIC) under suporevision of Prof. Dr. M. N. Sokolov. Now he is a researcher working in the Laboratory of synthesis of cooridnation compounds at NIIC. His research interests include synthesis of novel clusters and cluster complexes for the development of new materials.

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confidence: 99%

Molybdenum Iodides – from Obscurity to Bright Luminescence

Mikhaylov

Sokolov

2019

Eur J Inorg Chem

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“…, CO and nitriles). There are several reports involving the reactivity of the [Re 6 Se 8 (PEt 3 ) 5 (NCCH 3 )] 2+ ion, which involves a nucleophilic attack on the nitrile ligand, ,, demonstrating the highly Lewis acidic nature of this cluster core. In contrast, studies of the only other organometallic [Re 6 Se 8 ] 2+ -based complexes, [Re 6 Se 8 (PEt 3 ) 6– x (CO) x ](SbF 6 ) 2 ( x = 1–2), provide evidence of π-backbonding ( via IR spectroscopy and computational studies). , However, these interactions were deemed to be weak as the selenide atoms bonded to the rhenium atom of interest were major contributors to the orbitals involved in these interactions.…”

Section: Resultsmentioning

confidence: 99%

“…Only then can the full potential of these structures be realized. Studies over the past 20 years have provided us with a much better understanding about the solution phase chemistry of discrete [Mo 6 X 8 ] 4+ ( X = Cl, Br or I)- and [Re 6 Q 8 ] 2+ ( Q = S, Se or Te)-based systems. − However, the organometallic chemistry of these octahedral clusters is still in a nascent stage, with a limited number of organometallic ligands coordinated and studied. Zheng and co-workers succeeded in preparing the first organometallic rhenium selenide clusters, that is, [Re 6 Se 8 (PEt 3 ) 6– x (CO) x ] 2+ ( x = 1 or 2); computational studies indicate that the bridging selenides contribute electron density to the cluster–CO bonding interaction. , Our laboratory has been interested in expanding this field.…”

Section: Introductionmentioning

confidence: 99%

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

et al. 2022

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Three organometallic rhenium-based clusters containing phenylacetylide ligands, [Re 6 Se 8 (PEt 3 ) 5 (C�C−Ph)]-(SbF 6 ) (1) and cis-and trans-[Re 6 Se 8 (PEt 3 ) 4 (C�C−Ph) 2 ] (2 and 3), were synthesized and fully characterized including singlecrystal X-ray diffraction analyses. Reactivity studies of 1 show that reaction with electrophilic reagents does not result in the formation of the vinylidene species as predicted; instead, elimination of the acetylide moiety is observed. Products isolated from these r e a c t i o n s , i n c l u d i n g t h e m e t h y l s u l f a t e c o m p l e x , [Re 6 Se 8 (PEt 3 ) 5 (OSO 3 Me)](SbF 6 ) (4), have been characterized along with those obtained from the [2 + 2] cycloadditions of 1 with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane. The relative reactivities of the electrophilic agents utilized are compared. Preliminary computational studies reveal useful information about the nature of the [Re 6 Se 8 ] 2+ −acetylide bond and aid in our understanding of the reactivity associated with this cluster complex.

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“…Among such clusters, molybdenum compounds can be particularly distinguished, whose representatives have proven to be useful, for example, as agents in biology and medicine [ 6 ], components of optical materials [ 9 , 10 ], catalysts [ 11 ], etc. The most studied in these fields are the octahedral halide clusters [Mo 6 × 8 L 6 ] (X = Cl, Br, I; L = organic or inorganic ligands) [ 12 ] and the tri- and tetranuclear chalcogenide clusters with cluster cores {Mo 3 Q 7 }, {Mo 3 Q 4 } and {Mo 3 Q 4 M′} (Q = S, Se; M′ = Cu, Ni, Co, Fe, etc.) [ 4 , 11 ].…”

Section: Introductionmentioning

confidence: 99%

Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties

Savina,

Ivanov,

Eltsov

et al. 2023

IJMS

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The chemistry of transition metal clusters has been intensively developed in the last decades, leading to the preparation of a number of compounds with promising and practically useful properties. In this context, the present work demonstrates the preparation and study of the reactivity, i.e., the possibility of varying the ligand environment, of new square pyramidal molybdenum chalcogenide clusters [{Mo5(μ3-S)i4(μ4-S)i(μ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). The one-step synthesis starting from the octahedral Mo6Br12 cluster as well as the substitution of the apical pyrazole ligand or the selective bromination of the inner pyrazolate ligands were demonstrated. All the obtained compounds were characterized in detail using a series of physicochemical methods both in solid state (X-ray diffraction analysis, etc.) and in solution (nuclear magnetic resonance spectroscopy, mass spectrometry, etc.). In this work, redox properties and absorption in the ultraviolet-visible and near-infrared region of the obtained compounds were studied.

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Exploring the Breadth of Terminal Ligands Coordinated in [Mo6X8]4+- and [Re6Q8]2+-Based Cluster Complexes

Cited by 8 publications

References 100 publications

Molybdenum Iodides – from Obscurity to Bright Luminescence

Molybdenum Iodides – from Obscurity to Bright Luminescence

Rhenium Selenide Clusters Containing Alkynyl Ligands: Unexpected Reactivity of σ-Bound Phenylacetylide

Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties

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