Compounds with Two Metal−Metal Multiple Bonds:  New Ways of Making Doublets into Cyclic Quartets

Cotton, F. Albert; Daniels, Lee M.; Guimet, I.; Henning, Robert; Jordan, Glenn T.; Lin, Chiun-Yan; Murillo, Carlos A.; Schultz, Arthur J.

doi:10.1021/ja982425f

Cited by 33 publications

(49 citation statements)

References 34 publications

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“…Subsequently, however, it was noted that its two three‐centered, two‐electron (3c‐2e) Mo‐H‐Mo interactions were more in accordance with a Mo=Mo formulation [17] . Some tetranuclear complexes comprising two Mo≣Mo units bridged by hydride ligands and stabilized by coordination to p ‐aryl substituted formamidinate groups were reported by Cotton, Murillo, and co‐workers [18–21] . A few dimolybdenum hydride complexes with lower Mo−Mo bond orders have also been described [22–25] …”

Section: Introductionmentioning

confidence: 95%

Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands

Pérez‐Jiménez

Curado

Maya

et al. 2021

Chemistry A European J

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This contribution focuses on complex [Mo2(H)2(μ‐AdDipp2)2] (1) and tetrahydrofuran and pyridine adducts [Mo2(H)2(μ‐AdDipp2)2(L)2] (1⋅thf and 1⋅py), which contain a trans‐(H)Mo≣Mo(H) core (AdDipp2=HC(NDipp2)2; Dipp=2,6‐iPr2C6H3). Computational studies provide insights into the coordination and electronic characteristics of the central trans‐Mo2H2 unit of 1, with four‐coordinate, fourteen‐electron Mo atoms and ϵ‐agostic interactions with Dipp methyl groups. Small size C‐ and N‐donors give rise to related complexes 1⋅L but only one molecule of P‐donors, for example, PMe3, can bind to 1, causing one of the hydrides to form a three‐centered, two‐electron (3c‐2e) Mo‐H→Mo bond (2⋅PMe3). A DFT analysis of the terminal and bridging hydride coordination to the Mo≣Mo bond is also reported, along with reactivity studies of the Mo−H bonds of these complexes. Reactions investigated include oxidation of 1⋅thf by silver triflimidate, AgNTf2, to afford a monohydride [Mo2(μ‐H)(μ‐NTf2)(μ‐AdDipp2)2] (4), with an O,O’‐bridging triflimidate ligand.

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Section: Introductionmentioning

confidence: 95%

Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands

Pérez‐Jiménez

Curado

Maya

et al. 2021

Chemistry A European J

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“…In the same way, [Mo 2 (CH 3 COO) 4 ], Me 3 SiI and PBu 3 yield [(Mo 2 I 2 (PBu 3 ) 2 ) 2 (µ‐I) 4 ], where two Mo 4 2+ units share bridging iodides without additional Mo–Mo bonding between the dimers. The reaction is complete in two days at 0° C . When such powerful driving force as Si–O bond formation is absent, reactions with a source of I – stop after coordination at the axial position to the Mo–Mo bond, without actual ligand substitution, with the formation of [Mo 2 (CH 3 COO) 4 I 2 ] 2– or [Mo 2 (CF 3 COO) 4 I 2 ] 2– .…”

Section: Low Nuclearity Complexes and Clustersmentioning

confidence: 99%

“…When such powerful driving force as Si–O bond formation is absent, reactions with a source of I – stop after coordination at the axial position to the Mo–Mo bond, without actual ligand substitution, with the formation of [Mo 2 (CH 3 COO) 4 I 2 ] 2– or [Mo 2 (CF 3 COO) 4 I 2 ] 2– . Even formation of a Si–N bond appears profitable to ensure the transformation of [Mo 2 (DAniF) 4 ] (HDAniF = N , N′ ‐di‐ p ‐anisylformamidine) into a mixed‐ligand complex [(Mo 2 (DAniF) 2 ) 2 (µ‐I) 4 ] (0° C, 2 days, 94 %) . No tungsten analogues of these compounds have been reported.…”

Section: Low Nuclearity Complexes and Clustersmentioning

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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“…1 Among the types of assemblies that have now been described by various research groups are simple pairs of dimetal units connected by one 2, 3 or two 4 bridging ligands, molecular triangles, 5-8 squares, 5,9,10 complex polyhedra, 11 and three-dimensional networked arrays. 12 Inorganic ligands that have been used as connectors between dimetal units include the halides, 13-15 oxide, 16,17 carbonate anion, 18,19 hydride, 14,20 tetraoxo anions EO 4 2− (E = S, Mo. W), 21 and [M(OMe) 4 ] 2− (M = Zn, Co).…”

Section: Introductionmentioning

confidence: 99%

An unusual trigonal D3 assembly composed of molybdate anions and multiply bonded dimolybdenum units

Donahue

Murillo

2008

Dalton Trans.

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Oxidation of the molybdate-linked pair having two quadruply bonded Mo(2)(4+) units, [Mo(2)(DAniF)(3)](2)(micro(2)-MoO(4)), (DAniF = N,N'-di-(p-anisyl)formamidinate) leads to the formation of a species consisting of three oxidized Mo(2)(5+) units connected by two micro(3)-MoO(4)(2-) dianions, {[Mo(2)(DAniF)(3)](3)(micro(3)-MoO(4))(2)}(2+). This cation displays overall D(3) point group symmetry due to a slight twisting of the three Mo(2)(5+) units about the threefold symmetry axis. This distortion removes all mirror symmetry but preserves all C(2) axes orthogonal to the unique C(3) axis. Cyclic voltammetry of {[Mo(2)(DAniF)(3)](3)(micro(3)-MoO(4))(2)}(2+) in CH(2)Cl(2) reveals three reversible one-electron redox processes, corresponding to successive reduction of each of the three Mo(2)(5+) units, with DeltaE(1/2) separations of 0.36 V and 0.41 V.

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Compounds with Two Metal−Metal Multiple Bonds: New Ways of Making Doublets into Cyclic Quartets

Cited by 33 publications

References 34 publications

Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands

Experimental and Computational Studies on Quadruply Bonded Dimolybdenum Complexes with Terminal and Bridging Hydride Ligands

Molybdenum Iodides – from Obscurity to Bright Luminescence

An unusual trigonal D3 assembly composed of molybdate anions and multiply bonded dimolybdenum units

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