Group 13 Metal–Metal Bonds

Abdalla, Joseph A. B.; Aldridge, Simon

doi:10.1002/9783527673353.ch13

Cited by 11 publications

(6 citation statements)

References 317 publications

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“…The creation of new reactivities by metal mixing also entered the field of metal–metal bonding. [ 19 , 20 , 21 , 22 ] The unique reactivity of homometallic, low‐valent main group metal complexes can be further enriched by heterobimetallic metal–metal bound complexes. A most recent example represents the introduction of R 2 Al‐K reagents[ 23 , 24 , 25 , 26 , 27 , 28 , 29 ] which based on the metal's electronegativity differences should be classified as R 2 Al − K + reagents with nucleophilic aluminyl units (e.g.…”

Section: Introductionmentioning

confidence: 99%

Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

et al. 2021

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Low-valent ( Me BDI)Al and ( Me BDI)Ga and highly Lewis acidic cations in [( tBu BDI)M + •C 6 H 6 ][(B(C 6 F 5 ) 4 À ]( M= Mg or Zn, Me BDI = HC[C(Me)N-DIPP] 2 , tBu BDI = HC[C-(tBu)N-DIPP] 2 ,D IPP = 2,6-diisopropylphenyl) react to heterobimetallic cations [( tBu BDI)Mg-Al( Me BDI) + ], [( tBu BDI)Mg-Ga( Me BDI) + ]a nd [( tBu BDI)Zn-Ga( Me BDI) + ]. These cations feature long Mg-Al (or Ga) bonds while the Zn-Ga bond is short. The [( tBu BDI)Zn-Al( Me BDI) + ]c ation was not formed. Combined AIM and charge calculations suggest that the metal-metal bonds to Zn are considerably more covalent, whereas those to Mg should be described as weak Al I (or Ga I )!Mg 2+ donor bonds.F ailure to isolate the Zn-Al combination originates from cleavage of the C À Fb ond in the solvent fluorobenzene to give ( tBu BDI)ZnPh and ( Me BDI)AlF + which is extremely Lewis acidic and was not observed, but ( Me BDI)Al(F)-(m-F)-(F)Al( Me BDI) + was verified by X-ray diffraction. DFT calculations show that the remarkably facile C-F bond cleavage follows adearomatization/rearomatization route.

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Section: Introductionmentioning

confidence: 99%

Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

et al. 2021

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“…Common compounds with Group 13 elements as the central atom are designated as EX 3 (E = B, Al, Ga, In, Tl) and are known as electron-deficient compounds. Therefore, for bonds formed between a Group 13 element and a transition metal (TM), a TM→E dative bond can be considered in addition to a TM–E covalent bond (for example, TM–EX 2 ) ( Figure 1 shows an example in which E = In) [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. A normal bond between a TM and a ligand is formed by donating two electrons from the ligand to the TM.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of Molybdenum– and Tungsten–Indane Complexes with Tris(pyrazolyl)borate Ligand

Itazaki,

Nouichi,

Ookuma

et al. 2024

Molecules

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The reaction of molybdenum complexes with a tris(pyrazolyl)borate ligand (Et4N[TpMo(CO)3] and Et4N[Tp*Mo(CO)3] (Tp = hydridotris(pyrazolyl)borate, Tp* = hydridotris(3,5-dimethylpyrazolyl)borate)) and InBr3 at a 1:1 molar ratio afforded molybdenum–indane complexes (Et4N[TpMo(CO)3(InBr3)] 1 and Et4N[Tp*Mo(CO)3(InBr3)] 2). In addition, tungsten–indane complexes, Et4N[TpW(CO)3(InBr3)] 3 and Et4N[Tp*W(CO)3(InBr3)] 4, were obtained by the reaction of corresponding tungsten complexes. Complex 4 reacted with H2O to form the hydrido complex Tp*W(CO)3H, in which the W–In bond was cleaved. On the other hand, 4 reacted with three equiv. of AgNO3 to form Et4N[Tp*W(CO)3{In(ONO2)}] 5, in which three substituents on the In were exchanged while retaining the W–In dative bond. Complexes 1–5 were fully characterized using NMR measurements and elemental analyses, and the structures of 1–5 and Et4N[Tp*W(CO)3] were determined via X-ray crystallography. These are the first examples of mononuclear molybdenum– and tungsten–indane complexes with Mo–In and W–In dative bonds.

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“…Another class of reactive group 13 species emerges when [R 2 M • ] (M = group 13 metal) undergo reduction, forming anionic carbenoid [R 2 M:] − species. These anionic species find stabilization through various bisamido ligands, including diaminoxanthene ligands [13], NON-ligands (NON = [O(SiMe 2 NAr) 2 ] 2− ) [14], SiN Dipp (SiN Dipp = CH 2 SiMe 2 N(2,6-iPr 2 C 6 H 3 )) 2 , deprotonated β-diketiminate [15], 1,1,4,4tetrakis(trimethylsilyl)butane-1,4-diyl [16], and 1,4-diazadiene ligands [17][18][19][20][21][22]. Additionally, they can be part of cyclic(alkyl)(amino)aluminyl anions [23,24].…”

Section: Introductionmentioning

confidence: 99%

Reduction and Cycloaddition of Heteroalkenes at Ga(I) Bisamide Center

Dodonov,

Kushnerova,

Baranov

et al. 2024

Reactions

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The reactivity of the complex [(dpp-bian)GaNa(DME)2] (1) (dpp-bian = 1,2-bis[(2,6-di-isopropylphenyl)imino]acenaphthene) towards isocyanates, benzophenone, diphenylketene, and 1,2-dibenzylidenehydrazine has been studied. Treatment of 1 with isocyanates led to derivatives of imidoformamide [(dpp-bian)Ga{C(=NPh)2}2–NPh][Na(DME)3] (2), biuret [(dpp-bian)Ga(NCy)2(CO)2NCy][Na(DME)] (3), or carbamic acids [(dpp-bian)GaN(Cy)C(O)O]2[Na(THF)(Et2O)] (4), [(dpp-bian)GaC(=NCy)N(Cy)C(O)O][Na(Py)3] (5). Treatment of 1 with 2 equiv. of Ph2CO resulted in gallium pinacolate [(dpp-bian)GaO(CPh2)2O][Na(Py)2] (9), while the reaction of 1 with 2 equiv. Ph2CCO gave divinyl ether derivative [(dpp-bian)Ga{C(=CPh2)O}2][Na(DME)3] (10). Complex 1 treated with 2 equiv. 1,2-dibenzylidenehydrazine underwent [1+2+2] cycloaddition to give C–C coupling product [(dpp-bian)Ga{N(NCHPh)}2(CHPh)2][Na(DME)3] (11). When complex 1 was sequentially treated with 1 equiv. of 1,2-dibenzylidenehydrazine and 1 equiv. of pyridine or pyridine-d5; it gave [1+2+2] cycloaddition product [(dpp-bian)GaN(NCHPh)C(Ph)CN][Na(DME)3] (12). Compounds 2–12 were characterized by NMR and IR spectroscopy, and their molecular structures were established by single-crystal X-ray diffraction analysis.

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Group 13 Metal–Metal Bonds

Cited by 11 publications

References 317 publications

Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

Cationic Heterobimetallic Mg(Zn)/Al(Ga) Combinations for Cooperative C–F Bond Cleavage

Synthesis, Structure, and Reactivity of Molybdenum– and Tungsten–Indane Complexes with Tris(pyrazolyl)borate Ligand

Reduction and Cycloaddition of Heteroalkenes at Ga(I) Bisamide Center

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