Syntheses of N2-bridged heterobimetallic complexes, their structural and qualitative bonding analyses

Dé, Quentin Le; Orbay, Fourat; Vendier, Laure; Simonneau, Antoine

doi:10.1016/j.jorganchem.2022.122604

Cited by 3 publications

(5 citation statements)

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“…50,51 The X-ray structure of 6 is shown in 52 Moreover, Hidai et al synthesized a series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals. 30,31 These complexes can be regarded as formal [N 2 S13). The vanadium and chromium 2p XPS spectra show that the binding energies of complex 6 are 515.7 and 575.5 eV, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…For instance, Cummins et al reported the Mo–Ti μ-N 2 complex [(Ar[R]N) 3 Mo(μ-N 2 )Nb(N[ i Pr]Ar) 3 (R = t Bu or C(CD 3 ) 2 CH 3 )] (NN = 1.235(10) Å) . Moreover, Hidai et al synthesized a series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals. , These complexes can be regarded as formal [N 2 2– -bridged M1–N 2 –M2 complex, and their N–N distances fall within 1.21(2)∼1.275(9) Å. The UV–vis spectrum absorption bands of Cp*Cr(depe)(μ-N 2 )V(Et 2 O) Tipp [O, P, O] 6 are at 606 and 707 nm (Figure S13).…”

Section: Resultsmentioning

confidence: 99%

“…All chemical shifts were reported in units of parts per million with references to the residual protons of the deuterated solvents for proton chemical shifts and the 13 C of deuterated solvents for carbon chemical shifts. 31 P chemical shifts are reported in ppm relative to 85% aqueous H 3 PO 4 . 15 N chemical shifts are reported in ppm relative to liquid NH 3 at 0 ppm.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…The first involved the insertion of the M1–N 2 fragment into the metal-halide bonds of M2(X) to generate the M1(X)–N 2 –M2 complexes. Hidai et al and Simonneau et al reported a series of heterobimetallic μ-N 2 complexes, systematically synthesized through the reaction of end-on Mo 0 and W 0 dinitrogen complexes with high-valent organometallic halides. − The second approach was the transmetalation reaction, whereby the cation (Li or Mg) of a metal–dinitrogen complex was transformed into another metal through a transmetalation process. For example, in 1999, Schrock and co-workers demonstrated the preparation of heterobimetallic dinitrogen complex that contains the {[N 3 N]Mo–N 2 } − ligand by reacting {[N 3 N]Mo–N 2 } 2 Mg(THF) 2 with transition metal halides. , The third strategy pertained to the formation of formal Lewis pairs via coordination of Lewis acid complexes to the terminal TM–N 2 complexes.…”

Section: Introductionmentioning

confidence: 99%

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Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Wang,

et al. 2023

Inorg. Chem.

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In the domain of N2 activation, hetero-bimetallic dinitrogen complexes are garnering substantial interest due to their potential to induce polarization in nonpolar N2 gas. Herein, we present the syntheses and characterizations of three novel hetero-multimetallic dinitrogen complexes: Cp*Cr(depe)N2V(depe) Me [O, P, O] 5, Cp*Cr(depe)N2V(depe) Tipp [O, P, O] 6, and [Cp*Cr(depe)N2]2Ti Tipp [O, P, O] 7. These complexes were synthesized via a transmetalation process involving the treatment of [Cr0–N2]− complex 4 with vanadium and titanium chloride complexes bearing alkyl or aryl substituted bis(o-hydroxyphenyl)-phenyl phosphine R [O, P, O] ligand (alkyl = methyl, aryl = 2,4,6-tri-isopropylbenzene). X-ray analysis shows that complexes 5 and 6 exhibit heterodinuclear structures, while complex 7 exhibits a heterotrinuclear core with two N2 ligands concurrently coordinated to two chromium and one titanium atoms. Raman spectroscopic data show that the N–N stretching vibration of the N2 moiety is clearly downshifted relative to free N2 and to mononuclear [Cr0–N2]− complex 4.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Wang,

et al. 2023

Inorg. Chem.

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“…4,5 N 2 bridged heterometallic complexes were reported in seminal studies more than 50 years ago [6][7][8][9][10][11][12][13][14][15] but the use of mid-tolate d-elements such as iron 16,17 remains rare. Recently, N 2 bridged heterobimetallic complexes [18][19][20][21][22] have attracted increasing interest in transition metal chemistry for their potential to produce more polarized, and therefore more reactive, dinitrogen via a "push-pull" activation. 16,17,[23][24][25] However, Lewis acid-base interaction remains a difficult and underdeveloped route to the synthesis of heterobimetallic N 2 complexes.…”

Section: Introductionmentioning

confidence: 99%

Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of uranium and lanthanides

Jori,

Moreno,

Shivaraam

et al. 2024

Chem. Sci.

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Lewis Structures and the Bonding Classification of End-on Bridging Dinitrogen Transition Metal Complexes

et al. 2023

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The activation of dinitrogen by coordination to transition metal ions is a widely used and promising approach to the utilization of Earth’s most abundant nitrogen source for chemical synthesis. End-on bridging N2 complexes (μ-η1:η1-N2) are key species in nitrogen fixation chemistry, but a lack of consensus on the seemingly simple task of assigning a Lewis structure for such complexes has prevented application of valence electron counting and other tools for understanding and predicting reactivity trends. The Lewis structures of bridging N2 complexes have traditionally been determined by comparing the experimentally observed NN distance to the bond lengths of free N2, diazene, and hydrazine. We introduce an alternative approach here and argue that the Lewis structure should be assigned based on the total π-bond order in the MNNM core (number of π-bonds), which derives from the character (bonding or antibonding) and occupancy of the delocalized π-symmetry molecular orbitals (π-MOs) in MNNM. To illustrate this approach, the complexes cis,cis-[(iPr4PONOP)MCl2]2(μ-N2) (M = W, Re, and Os) are examined in detail. Each complex is shown to have a different number of nitrogen–nitrogen and metal–nitrogen π-bonds, indicated as, respectively: WN–NW, ReNNRe, and Os–NN–Os. It follows that each of these Lewis structures represents a distinct class of complexes (diazanyl, diazenyl, and dinitrogen, respectively), in which the μ-N2 ligand has a different electron donor number (total of 8e–, 6e–, or 4e–, respectively). We show how this classification can greatly aid in understanding and predicting the properties and reactivity patterns of μ-N2 complexes.

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Syntheses of N2-bridged heterobimetallic complexes, their structural and qualitative bonding analyses

Cited by 3 publications

References 49 publications

Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Syntheses and Characterizations of Hetero-Bimetallic Chromium-Dinitrogen Transition-Metal Complexes

Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of uranium and lanthanides

Lewis Structures and the Bonding Classification of End-on Bridging Dinitrogen Transition Metal Complexes

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