Molecular Lanthanoid–Transition‐Metal Cluster through CH Bond Activation by Polar Metal–Metal Bonds

Butovskii, Mikhail V.; Tok, Oleg L.; Bezugly, Viktor; Wagner, Frank R.; Kempe, Rhett

doi:10.1002/anie.201102363

Cited by 35 publications

(20 citation statements)

References 36 publications

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“…Systematic position‐space analysis of T − R bonding ( T =transition metal species) has started with the observation of Mo−4La polyatomic ELF (electron localization function) basin in the carbometallate La 2 [MoC 2 ] . In subsequent studies on bi‐, tri‐, tetra‐ and pentametallic organometallic clusters, most of them featuring unsupported T − R bonding signified by an ELI‐D attractor close to the internuclear line, the picture of a chemically significant bonding interaction could be established . It has been described as the polar‐covalent interaction between an electron‐rich transition metal species T acting as the Lewis base, and a Lewis acidic rare earth species R .…”

Section: Resultsmentioning

confidence: 99%

“…. [39] In subsequent studies on bi-, [40] tri-, [41] tetra- [42] and pentametallic [43] organometallic clusters, most of them featuring unsupported TÀR bondings ignified by an ELI-D attractor close to the internuclear line, the pictureo f ac hemically significant bonding interaction could be established. [44] It has been described as the polar-covalenti nteraction between an electron-rich transition metal species T acting as the Lewis base, and aL ewis acidic rare earth species R. Transfero ft his picture to TÀR bondingi ni ntermetallic phases www.chemeurj.org has been performedi np arallel.…”

Section: LImentioning

confidence: 99%

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Polar‐Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare‐Earth Germanides

Freccero

Solokha

Negri

et al. 2019

Chemistry A European J

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A comparative chemical bonding analysis for the germanides La2MGe6 (M=Li, Mg, Al, Zn, Cu, Ag, Pd) and Y2PdGe6 is presented, together with the crystal structure determination for M=Li, Mg, Cu, Ag. The studied compounds adopt the two closely related structure types oS72‐Ce2(Ga0.1Ge0.9)7 and mS36‐La2AlGe6, containing zigzag chains and corrugated layers of Ge atoms bridged by M species, with La/Y atoms located in the biggest cavities. Chemical bonding was studied by means of the quantum chemical position‐space techniques QTAIM (quantum theory of atoms in molecules), ELI‐D (electron localizability indicator), and their basin intersections. The new penultimate shell correction (PSC0) method was introduced to adapt the ELI‐D valence electron count to that expected from the periodic table of the elements. It plays a decisive role to balance the Ge−La polar‐covalent interactions against the Ge−M ones. In spite of covalently bonded Ge partial structures formally obeying the Zintl electron count for M=Mg2+, Zn2+, all the compounds reveal noticeable deviations from the conceptual 8−N picture due to significant polar‐covalent interactions of Ge with La and M ≠ Li, Mg atoms. For M=Li, Mg a formulation as a germanolanthanate M[La2Ge6] is appropriate. Moreover, the relative Laplacian of ELI‐D was discovered to reveal a chemically useful fine structure of the ELI‐D distribution being related to polyatomic bonding features. With the aid of this new tool, a consistent picture of La/Y−M interactions for the title compounds was extracted.

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Section: Resultsmentioning

confidence: 99%

Section: LImentioning

confidence: 99%

Polar‐Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare‐Earth Germanides

Freccero

Solokha

Negri

et al. 2019

Chemistry A European J

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“…A powerful alternative method for the generation of discrete Ln−TM bonded molecular species was introduced in 2008 by Kempe and co‐workers, who established the versatile utility of alkane elimination reactions between Ln–alkyl and acidic TM–hydride species . This method was also exploited to generate a Lu−Re bonded species, and was further shown to enable the formation of remarkable complexes that feature three intramolecular Ln−Re bonds (Ln=Sm, Lu, La) …”

Section: Methodsmentioning

confidence: 99%

Structure and Magnetization Dynamics of Dy−Fe and Dy−Ru Bonded Complexes

et al. 2018

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We present an investigation of isostructural complexes that feature unsupported direct bonds between a formally trivalent lanthanide ion (Dy3+) and either a first‐row (Fe) or a second‐row (Ru) transition metal (TM) ion. The sterically rigid, yet not too bulky ligand PyCp22− (PyCp22−=[2,6‐(CH2C5H3)2C5H3N]2−) facilitates the isolation and characterization of PyCp2Dy−FeCp(CO)2 (1; d(Dy–Fe)=2.884(2) Å) and PyCp2Dy−RuCp(CO)2 (2; d(Dy–Ru)=2.9508(5) Å). Computational and spectroscopic studies suggest strong TM→Dy bonding interactions. Both complexes exhibit field‐induced slow magnetic relaxation with effectively identical energy barriers to magnetization reversal. However, in going from Dy−Fe to Dy−Ru bonding, we observed faster magnetic relaxation at a given temperature and larger direct and Raman coefficients, which could be due to differences in the bonding and/or spin–phonon coupling contributions to magnetic relaxation.

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“…Kempe extended the chemistry of 17 by reporting the synthesis of another complex containing a Lu-Re bond ( Figure 4 ) (Butovskii et al 2011 Figure 3 Complexes 10 -14 .…”

Section: Lanthanide-transition Metal Complexesmentioning

confidence: 97%

f-Element-metal bond chemistry

Patel

Liddle

2012

Reviews in Inorganic Chemistry

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Compared to the overwhelming prevalence of f-elementcarbon, -nitrogen, -oxygen or -halide ligand linkages, the use of metal-based fragments as ligands is underdeveloped. This contrasts directly to the extensively developed fi elds of d-and p-block metal-metal complexes, which are still burgeoning. This review outlines the development of compounds that possess polarised covalent f-element-metal bonds. For this review, the f-element is defi ned as (i) a group 3 metal; (ii) a lanthanide metal; (iii) the actinide metals thorium or uranium. The metal is defi ned as: (i) a d-block transition metal; (ii) a group 13 metal (aluminium or gallium); (iii) a group 14 metal (silicon, germanium or tin); (iv) a group 15 metal (antimony or bismuth) metal. Although silicon, germanium and antimony are traditionally classifi ed as metalloids, they are included for completeness. We focus on complexes that have been structurally authenticated by single crystal X-ray diffraction, and we highlight novel aspects of their syntheses, properties and reactivities.

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Molecular Lanthanoid–Transition‐Metal Cluster through CH Bond Activation by Polar Metal–Metal Bonds

Cited by 35 publications

References 36 publications

Polar‐Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare‐Earth Germanides

Polar‐Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare‐Earth Germanides

Structure and Magnetization Dynamics of Dy−Fe and Dy−Ru Bonded Complexes

f-Element-metal bond chemistry

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