Zweifach koordinierte Übergangsmetallzentren mit Metall‐Metall‐Bindungen

Holland, Patrick L.

doi:10.1002/ange.201101209

Cited by 2 publications

(2 citation statements)

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“…[2d, 14] For strongly polar heteronuclear metal-metal bonds that comprise two very different metal centres with complementary ligand sets, the term xenophilic bonds has been coined. [15] Typically, one metal atom in a low formal oxidation state stabilised by s-donor/p-acceptor ligands forms a more or less polar bond to a metal centre in a higher oxidation state that bears either anionic or neutral donor ligands (selected examples are outlined in Figure 1). …”

Section: Introductionmentioning

confidence: 99%

“…(204.7 pm), [15] [MgBr(thf) 4 {6-[(Me 6 B 3 N 3 )Cr(CO) 3 }] (207.9 pm), [23] and [Mg(thf) 2 {m-Cym*C(BC 4 Ph 4 ) 2 }Mg(thf) 3 ] (219.4 pm). [24] In good agreement with the IR spectroscopic data, the atomic distances of the CÀ O bonds in the isocarbonyl bridges (average bond length = 120.8 (3 a) and 119.6 pm (3 b)) are approximately 3 pm longer than in the terminal CO ligands (average bond length 116.9 (3 a) and 117.1 pm (3 b)).…”

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confidence: 99%

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Tris(3,5‐dimethylpyrazolyl)methane‐Based Heterobimetallic Complexes that Contain Zn and CdTransition‐Metal Bonds: Synthesis, Structures, and Quantum Chemical Calculations

Meyer

González‐Gallardo

Hohnstein

et al. 2014

Chemistry A European J

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Reactions of the tris(3,5-dimethylpyrazolyl)methanide amido complexes [M'{C(3,5-Me2 pz)3 }{N(SiMe3 )2 }] (M'=Mg (1 a), Zn (1 b), Cd (1 c); 3,5-Me2 pz=3,5-dimethylpyrazolyl) with two equivalents of the acidic Group 6 cyclopentadienyl (Cp) tricarbonyl hydrides [MCp(CO)3 H] (M=Cr (2 a), Mo (2 b)) gave different types of heterobimetallic complex. In each case, two reactions took place, namely the conversion of the tris(3,5-dimethylpyrazolyl)methanide ligand (Tpmd*) into the -methane derivative (Tpm*) and the reaction of the acidic hydride M = H bond with the M' = N(SiMe3 )2 moiety. The latter produces HN(SiMe3 )2 as a byproduct. The Group 2 representatives [Mg(Tpm*){MCp(CO)3 }2 (thf)] (3 a/b) form isocarbonyl bridges between the magnesium and chromium/molybdenum centres, whereas direct metal-metal bonds are formed in the case of the ions [Zn(Tpm*){MCp(CO)3 }](+) (4 a/b; [MCp(CO)3 ](-) as the counteranion) and [Cd(Tpm*){MCp(CO)3 }(thf)](+) (5 a/b; [Cd{MCp(CO)3 }3 ](-) as the counteranion). Complexes 4 a and 5 a/b are the first complexes that contain Zn - Cr, Cd - Cr, and Cd - Mo bonds (bond lengths 251.6, 269.8, and 278.9 pm, respectively). Quantum chemical calculations on 4 a/b* (and also on 5 a/b*) provide evidence for an interaction between the metal atoms.

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Section: Introductionmentioning

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Tris(3,5‐dimethylpyrazolyl)methane‐Based Heterobimetallic Complexes that Contain Zn and CdTransition‐Metal Bonds: Synthesis, Structures, and Quantum Chemical Calculations

Meyer

González‐Gallardo

Hohnstein

et al. 2014

Chemistry A European J

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Spin States, Bonding and Magnetism in Mixed‐Valence Iron(0)‐Iron(II) Complexes**

Kim

Wilson

Fataftah

et al. 2022

Chemistry A European J

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We report the synthesis of two complexes featuring unsupported Fe-Fe bonds, L x Fe-Fp (L a = 3-methyl-2,4-bis(2,6-dimethylphenylimido)pentyl, L b = 1,3-bis (2,4,6trimethylphenylimido)propyl; Fp = Fe(CO)2Cp). Mössbauer spectroscopy, SQUID magnetometry and computational analysis indicate that the most accurate electronic structure description is LFe II -Fe 0 (CO)2Cp, in which the Fe(CO)2Cp is low spin iron(0) and acts as a Lewis base toward the high spin iron(II) of the LFe fragment which is a Lewis acid. In both compounds, the three-coordinate high-spin iron(II) site has large zero-field splitting (zfs), up to D = -50 cm -1 .

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Zweifach koordinierte Übergangsmetallzentren mit Metall‐Metall‐Bindungen

Cited by 2 publications

References 28 publications

Tris(3,5‐dimethylpyrazolyl)methane‐Based Heterobimetallic Complexes that Contain Zn and CdTransition‐Metal Bonds: Synthesis, Structures, and Quantum Chemical Calculations

Tris(3,5‐dimethylpyrazolyl)methane‐Based Heterobimetallic Complexes that Contain Zn and CdTransition‐Metal Bonds: Synthesis, Structures, and Quantum Chemical Calculations

Spin States, Bonding and Magnetism in Mixed‐Valence Iron(0)‐Iron(II) Complexes**

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