Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes

Carrasco, Mario; Curado, Natalia; Álvarez, Eleuterio; Maya, Celia; Peloso, Riccardo; Poveda, Manuel L.; Rodríguez, Amor; Ruiz, Eliseo; Álvarez, Santiago; Carmona, Ernesto

doi:10.1002/chem.201400236

Cited by 34 publications

(20 citation statements)

References 75 publications

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“…As mentioned above, complex 1⋅thf was previously prepared by our group for specific synthetic purposes [28] . It was obtained from [Mo 2 (μ‐OAc) 2 (μ‐Ad Dipp2 ) 2 ] and an excess of LiMe, followed by elimination of LiMe from the intermediate complex [Mo 2 (μ‐Me){(μ‐Me) 2 Li(thf)}(μ‐Ad Dipp2 ) 2 ] and hydrogenolysis of the resulting neutral dimethyl [Mo 2 (Me) 2 (μ‐Ad Dipp2 ) 2 (thf)] [27] .…”

Section: Resultsmentioning

confidence: 99%

“…In addition, other complexes with terminal and bridging hydride ligands are described, along with studies on the activation of H 2 , CO 2 , and CS 2 by some of these complexes. We note that complex 1⋅thf was described by our group in the course of studies on arene adducts [28] of the quintuple Mo−Mo bond in [Mo 2 (μ‐Ad Dipp2 ) 2 ] [29] …”

Section: Introductionmentioning

confidence: 89%

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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: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 89%

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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“…Identification of the individual components of the above mixtures of products by multinuclear NMR spectroscopy was straightforward. Thus, complexes 3⋅THF , 3⋅PMe 3 , 5⋅THF , and 5⋅PMe 3 (in the pertinent isotopologue forms) were authenticated by comparison of their NMR parameters with those of authentic samples . Signature NMR data for the pursued intermediates 6⋅THF and 6⋅PMe 3 provided strong support for the hydride‐methyl formulation proposed in Scheme .…”

Section: Resultsmentioning

confidence: 99%

An Unsaturated Four‐Coordinate Dimethyl Dimolybdenum Complex with a Molybdenum–Molybdenum Quadruple Bond

Curado

Carrasco

Campos

et al. 2016

Chemistry A European J

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We describe the synthesis and the molecular and electronic structures of the complex [Mo Me {μ-HC(NDipp) } ] (2; Dipp=2,6-iPr C H ), which contains a dimetallic core with an Mo-Mo quadruple bond and features uncommon four-coordinate geometry and has a fourteen-electron count for each molybdenum atom. The coordination polyhedron approaches a square pyramid, with one of the molybdenum atoms nearly co-planar with the basal square plane, in which the trans coordination position with respect to the Mo-Me bond is vacant. The other three sites are occupied by two trans nitrogen atoms of different amidinate ligands and the methyl group. The second Mo atom occupies the apex of the pyramid and forms an Mo-Mo bond of length 2.080(1) Å, consistent with a quadruple bond. Compound 2 reacts with tetrahydrofuran (THF) and trimethylphosphine to yield the mono-adducts [Mo Me(μ-Me){μ-HC(NDipp) } (L)] (3⋅THF and 3⋅PMe , respectively) with one terminal and one bridging methyl group. In contrast, 4-dimethylaminopyridine (dmap) forms the bis-adduct [Mo Me {μ-HC(NDipp) } (dmap) ] (4), with terminally coordinated methyl groups. Hydrogenolysis of complex 2 leads to the bis(hydride) [Mo H {μ-HC(NDipp) } (thf) ] (5⋅THF) with elimination of CH . Computational, kinetic, and mechanistic studies, which included the use of D and of complex 2 labelled with C (99 %) at the Mo-CH sites, supported the intermediacy of a methyl-hydride reactive species. A computational DFT analysis of the terminal and bridging coordination of the methyl groups to the Mo≣Mo core is also reported.

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“…X‐ray crystallographic analysis on 12a and 12b revealed the temperature‐dependent molecular motion. In light of the remarkable reactivity of the type II quintuple‐bonded compounds, the characterization of 5 – 11 bodes well for a systematic reactivity study of these medium‐coordinate univalent dichromium complexes.…”

Section: Discussionmentioning

confidence: 92%

Chromium to chromium quintuple bonds in a trigonal lantern configuration

Yen

Lin

Hsueh

et al. 2019

J Chinese Chemical Soc

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A new family of the quintuply bonded dichromium complexes [Cr2{μ‐κ2‐HC(N‐2,6‐R2C6H3)2}2(μ‐κ2‐HC[NAr]2)] (R = iPr, Ar = 4‐MeC6H4 (5), Ar = 3,5‐Me2C6H3 (6), and Ar = 2,6‐Me2C6H3 (7); R = Et, Ar = 4‐MeC6H4 (8), Ar = 3,5‐Me2C6H3 [9], and Ar = 2,6‐Et2C6H3 (10)) with a heteroleptic lantern configuration was obtained upon the addition of one equivalent of amidinate to the quintuply bonded dichromium amidinates [Cr{μ‐κ2‐HC(N‐2,6‐R2C6H3)2}]2 (R = iPr, Et). Additionally, the same approach was applied to the preparation of the acetate derivative [Cr2{μ‐κ2‐HC(N‐2,6‐ iPr2C6H3)2}2(μ‐κ2‐CH3CO2)] (11), which represents the first example that the quintuply bonded dinuclear complex contains an oxygen‐containing ligand. Of particular interest is that the Cr‐Cr bond lengths in these new trigonal paddlewheel quintuple Cr‐Cr bond species are comparable with those in their precursor compounds. They show ultrashort Cr‐Cr bond lengths in a narrow range of 1.740–1.755 å on the basis of single‐crystal X‐ray crystallography. The small Mayer bond orders of the long Cr‐N bonds as well as divergent, C2v and D3h, structural conformations in 5–11 suggest that the metal–ligand interactions possess minor covalent character and the electrostatic interactions play a dominant role. As a result, these extremely short Cr‐Cr quintuple bonds are caused by the overlap between five pairs of d orbitals that do not involve much in metal–ligand bonding. Additionally, anionic lantern dichromium trisamidinates 5–10 can be chemically oxidized by one electron, supported by electrochemistry, and their ease to undergo oxidation is presumably associated with their neutral lantern dichromium trisamindinate products, whose structures inherently display a Jahn‐Teller distortion, exemplified by the structure of the homoleptic dichromium complex [Cr2{μ‐κ2‐HC(N‐2,6‐Et2C6H3)2}3] [12] determined by X‐ray crystallography. These results unambiguously support the Cr‐Cr quintuple bonding in these novel anionic lantern dichromium complexes.

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Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes

Cited by 34 publications

References 75 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

An Unsaturated Four‐Coordinate Dimethyl Dimolybdenum Complex with a Molybdenum–Molybdenum Quadruple Bond

Chromium to chromium quintuple bonds in a trigonal lantern configuration

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