Aryl(dimethyl)gallium Compounds and Methyl(diphenyl)gallium: Synthesis, Structure, and Redistribution Reactions

Jutzi, Peter; Izundu, Joseph; Neumann, Beate; Mix, Andreas; Stammler, Hans‐Georg

doi:10.1021/om701055a

Cited by 7 publications

(20 citation statements)

References 31 publications

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“…Hence, the transient cleavage product MeGaPh 2 engages in weak interactions with Cp* 2 YMe(THF) rather than with THF (Scheme b). Additionally, redistribution reactions could lead to the formation of GaPh 3 , Me 2 GaPh, and GaMe 3 , as previously reported for Me 2 GaPh . The latter two compounds are more prone to donor adduct formation, which could be a possible stimulus for ligand rearrangement reactions.…”

Section: Resultssupporting

confidence: 53%

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The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)

et al. 2021

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Yttrocene derivatives [Cp* 2 Y(MMe 4 )] (Cp* = C 5 Me 5 ; M = Al, Ga) and Cp* 2 Y[Me 3 Al{B(NDippCH) 2 }] (Dipp = C 6 H 3 iPr 2 -2,6) deprotonate benzene at elevated temperatures via the release of methane. The formation of [Cp* 2 Y(Me 2 MPh 2 )] (M = Al, Ga), Cp* 2 Y(MPh 4 ) (M = Al, Ga), Cp* 2 Y[Me 2 AlPh{B(NDippCH) 2 }], and Cp* 2 Y[AlPh 3 {B(NDippCH) 2 }] can be controlled via the temperature applied. The activation temperature and formation of the coordinatively unsaturated "reactive" [Cp* 2 YMe] strongly depend on the coordination strength of the displaceable Lewis acids [AlMe 3 ] 2 , GaMe 3 , and [Me 2 Al{B(NDippCH) 2 }] 2 . Hence, [Cp* 2 Y(AlMe 4 )] requires temperatures above 100 °C to metalate benzene, while Cp* 2 Y[AlMe 3 {B(NDippCH) 2 }] undergoes C−H-bond activation even at ambient temperatures. A kinetic deuterium isotope effect was observed for the reactions in C 6 D 6 solutions. Distinct differences in the stabilities of the bulky Group 13 anions ([Me 2 MPh 2 ] − , [MPh 4 ] − , [Me 3 Al{B(NDippCH) 2 }] − , [Me 2 AlPh{B(NDippCH) 2 }] − , and [AlPh 3 {B(NDippCH) 2 }] − ) are assessed by detailed studies of the coordination chemistry with tetrahydrofuran (THF) and by variable-temperature 1 H NMR spectroscopy. Thus, increased steric bulk or a reduced Lewis acidity of the Group 13 metal center promote temperature-sensitive dissociation of trivalent Group 13 alkyl entities. Consequently, compound Cp* 2 Y[AlPh 3 {B(NDippCH) 2 }] was found to engage in a dissociation equilibrium with [Cp* 2 YPh] and AlPh 2 {B(NDippCH) 2 } in a C 6 D 6 solution at ambient temperature. The reaction of Cp* 2 Y[AlPh 3 {B-(NDippCH) 2 }] with THF results in the concomitant formation of monometallic Cp* 2 YPh(THF) and the solvent-separated ion pair [Cp* 2 Y(THF) 2 ][AlPh 3 {B(NDippCH) 2 }].

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Section: Resultssupporting

confidence: 53%

“…Additionally, redistribution reactions could lead to the formation of GaPh 3 , Me 2 GaPh, and GaMe 3 , as previously reported for Me 2 GaPh. 79 The latter two compounds are more prone to donor adduct formation, which could be a possible stimulus for ligand rearrangement reactions. The 14).…”

Section: Metalation Of Benzene Bymentioning

confidence: 99%

The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)

et al. 2021

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“…The strategy for the synthesis of the dimethylgallyl-functionalized benzene derivatives is described in eq . The reaction sequence starts with the substitution of trimethylstannyl groups in the corresponding trimethylstannylbenzenes by chloromercurio groups, which subsequently are replaced by dimethylgallyl groups . Table shows the compounds involved in the synthetic procedure.…”

Section: Resultsmentioning

confidence: 99%

“…Surprisingly, the first monodimethylgallyl-substituted benzenes were described only recently. They show the expected substituent redistribution reactions . Here we describe the first multiple dimethylgallyl-substituted compounds with the synthesis of the 1,3-disubstituted derivatives 5 and 6 , of the 1,4-disubstituted derivative 9 , and of the 1,3,5-trisubstituted derivative 12 .…”

Section: Introductionmentioning

confidence: 97%

Bis- and Tris(dimethylgallyl)benzenes: Synthesis, Solid-State Structures, and Redistribution Reactions

et al. 2009

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Benzene derivatives containing dimethylgallyl substituents in 1,3-( compounds 5 and 6), 1,4-(compound 9), and 1,3,5-position (compound 12) were prepared by reaction of the corresponding chloromercuriobenzenes with an excess of trimethylgallium at higher temperatures. These compounds decompose in solution at room temperature and in the solid state upon mild heating with elimination of trimethylgallium to give oligomeric condensation products of unknown detailed composition. These condensation products can be transformed back into the starting compounds by treatment with an excess of trimethylgallium at higher temperatures. Highly air-sensitive crystals of 5, 6, 9, and 12 suitable for an X-ray analysis are obtained from trimethylgallium as solvent. The X-ray crystallographic studies revealed the presence of higher coordinate gallium atoms, which lead to the formation of strand-or sheet-like polymers. A trigonalbipyramidal coordination sphere is observed for the gallium atoms in 9. A distorted tetrahedral coordination is found for the gallium atoms in 5, 6, and 12. The latter compounds possess asymmetric aryl-dimethylgallyl bridging units.

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“…The molecular structures show the gallium atoms as trigonal planar with additional Z 1 contacts with the phenyl rings stacked above and below. 94 Reaction of [Ru(GaCp*) 3…”

Section: Methodsmentioning

confidence: 99%

Aluminium, gallium, indium and thallium

López

2009

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Aryl(dimethyl)gallium Compounds and Methyl(diphenyl)gallium: Synthesis, Structure, and Redistribution Reactions

Cited by 7 publications

References 31 publications

The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)

The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)

Bis- and Tris(dimethylgallyl)benzenes: Synthesis, Solid-State Structures, and Redistribution Reactions

Aluminium, gallium, indium and thallium

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Aryl(dimethyl)gallium Compounds and Methyl(diphenyl)gallium: Synthesis, Structure, and Redistribution Reactions

Cited by 7 publications

References 31 publications

The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*2Y(MMe3R)] (M = Al, Ga)

The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*2Y(MMe3R)] (M = Al, Ga)

Bis- and Tris(dimethylgallyl)benzenes: Synthesis, Solid-State Structures, and Redistribution Reactions

Aluminium, gallium, indium and thallium

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The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)

The Alkylaluminate/Gallate Trap: Metalation of Benzene by Heterobimetallic Yttrocene Complexes [Cp*₂Y(MMe₃R)] (M = Al, Ga)