Group 13−Group 13 Donor−Acceptor Complexes

Abstract

Group 13-group 13 donor-acceptor complexes Cp*M-Al(t-Bu) 3 (M ) Al 1, Ga 2, In 3) and Cp*M-Ga(t-Bu) 3 (M ) Al 4, Ga 5, In 6) were obtained from reactions between [Cp*M] x (M ) Al, x ) 4; Ga, In, x ) 6) and M(t-Bu) 3 (M ) Al, Ga). 3, 4, and 6 represent the first compounds containing dative In(I)-Al(III), Al(I)-Ga(III), and In(I)-Ga(III) bonds. 1-6 were characterized by elemental analyses, mass and multinuclear NMR spectroscopy ( 1 H, 13 C), and single-crystal X-ray analysis (except for 5).Supporting Information Available: Tables of bond distances, bond angles, anisotropic temperature factor parameters, and fractional coordinates for 1, 2, 3, 4, and 6. This material is available free of charge via the Internet at http://pubs.acs.org. OM0606946

Lewis acid–base adducts of group 13 elements: synthesis, structure and reactivity toward benzaldehyde

“…III bond length of 2 (2.5482(4) Å) is in between those that reported for Cp*Ga-AlR 3 {R = t-Bu (2.629(2) Å), [14] C 6 F 5 (2.515(11) Å)}, [20] while the Ga I -Ga III bond length in 3 (2.4819(2) Å) is comparable to those observed in CpGa-GaCp 2 I (2.4690(17) Å), [21] [HB(3,5-(CF 3 ) 2 Pz) 3 ]Ga-GaI 3 (2.494(2) Å), [22] [HB(3,5-(t-Bu) 2 Pz) 3 ]Ga-GaI 3 (2.506(3) Å). [23] In contrast, those reported for [Tm [24] Cp*Ga-Cp*GaX 2 {X = Cl, 2.4245(3); I, 2.437(2) Å}, [25] [HB(3,5- [26] In addition, the Ga I -M III bond lengths in 2 (2.5482(4) Å) and 3 (2.4819(2) Å) slightly deviate from the sum of the covalent radii (single-bond covalent radii of Al 1.26 Å, Ga 1.24 Å).…”

“Crowned” Univalent Indium Complexes as Donors? Experimental and Computational Insights on the Valence Isomers of EE′X4 Species

“…Numerous examples of Group 13 pentamethylcyclopentadienyl complexes, Cp*E (E = Al, Ga, In), acting as donors to both transition metals and main group Lewis acids have been reported. [14,[16][17][18][19] Similarly, tris(pyrazolyl)borate ligands and a similar tris(2-mercapto-1-tert-butylimidazolyl) borate have also been shown to ligate Group 13 metal centers and lead to a complex with a reactive lone pair of electrons suitable for donation to appropriate acceptors. [20][21][22] Another family of donors that has yielded many donor-acceptor complexes are the Group 13 analogues of N-heterocyclic carbenes.…”

“…In most of these cases, the direct reaction of stable univalent Group 13 reagents such as those supported by Cp* ligands, b-diketiminate ligands, or bulky terphenyl ligands with Group 13 Lewis acids provides the anticipated donor-acceptor adducts in quantitative yield. [14] One final observation about the use of crown ethers as stabilizing ligands for In I fragments must be emphasized: whereas the complex of InOTf with [18]crown-6 is stable in the solid state and in many solvents, all attempts to stabilize indium(+1) halides using crown ethers have resulted in the rapid disproportionation of the compound with the concomitant deposition of indium metal.…”

“…[57] The computational investigations described above provide insight into our experimental observation of indiumÀindium donor-acceptor complexes such as 3-5, however we also wished to rationalize the non-observation of analogous mixed Group 13 metal species. To this end, full geometry optimizations and NBO analyses were performed on models of 3, and the putative donor-acceptor isomers of 9 and 10, that is, [Cl( [18]crown-6)InÀECl 3 ] (E= Al (14), Ga (15), In (3' opt ) illustrated in Figure 8). Selected results from the calculations are presented in Table 5.…”

Spin-Spin Coupling Constants 1J(27Al,13C) and 1J(13C,11B) in Comparable Organoaluminum and -boron Compounds. NMR Spectroscopy of Lithium Tetra(tert-butyl)alanate

“…Numerous adducts of 1 have been studied by 1 H and 13 C NMR [11], and again information on line shapes is missing. This is also true for Li[AlBu t 4 ] 5 [8].…”