Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear ((1) H, (13) C, and (71) Ga) solid-state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga-Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two-dimensional (71) Ga J/D-resolved NMR experiments which provide a direct measurement of J((71) Ga,(71) Ga) spin-spin coupling constants across the gallium-gallium bonds. When placed in the context of clear-cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the (71) Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane-gallene-gallyne series for classical and/or slipped π-type bonding orbitals.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/chem.201600999 | DOI Listing |
IUCrdata
July 2024
PO Box 6949, Radford University, Radford, Virginia 24142, USA.
The title compound, [RuGaCl(CH)(CO)] or [(CO)(GaCl)(η-toluene)Ru][GaCl], was isolated from the reaction of GaCl with di-phenyl-silanediol in toluene, followed by the addition of Ru(CO). The compound contains a ruthenium-gallium metal-metal bond with a length of 2.4575 (2) Å.
View Article and Find Full Text PDFChemistry
June 2019
G. A. Razuvaev Institute of Organometallic Chemistry, of Russian Academy of Sciences, Tropinina str. 49, Nizhny Novgorod, 603137, Russia.
Digallane [L Ga-GaL ] (1, L =dpp-bian=1,2-[(2,6-iPr C H )NC] C H ) reacts with RN=C=O (R=Ph or Tos) by [2+4] cycloaddition of the isocyanate C=N bonds across both of its C=C-N-Ga fragments to afford [L (O=C-NR)Ga-Ga(RN-C=O)L ] (R=Ph, 3; R=Tos, 4). The reactions with both isocyanates result in new C-C and N-Ga single bonds. In the case of allyl isocyanate, the [2+4] cycloaddition across one C=C-N-Ga fragment of 1 is accompanied by insertion of a second allyl isocyanate molecule into the Ga-N bond of the same fragment to afford compound [L Ga-Ga(AllN- C=O) L ] (5) (All=allyl).
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
September 2018
Naturhistorisches Museum Wien, Burgring 7, 1010 Wien, and Institut für Mineralogie und Kristallographie, Universität Wien, Althanstrasse 14, 1090 Wien, Austria.
The crystal structures of hydro-thermally synthesized ( = 493 K, 7-9 d) rubidium gallium bis-[hydrogenarsenate(V)], RbGa(HAsO), and rubidium digallium arsenic(V) hexa-[hydrogenarsenate(V)], RbGaAs(HAsO), were solved by single-crystal X-ray diffraction. Both compounds have tetra-hedral-octa-hedral framework topologies. The cations are located in channels of the respective framework.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
August 2018
Naturhistorisches Museum, Burgring 7, 1010 Wien, Austria.
The crystal structures of hydro-thermally synthesized ( = 493 K, 7 d) thallium(I) digallium arsenic(V) hexa-kis-[hydrogenarsenate(V)], TlGaAs(HAsO), caes-ium digallium arsenic(V) hexa-kis-[hydrogenarsenate(V)], CsGaAs(HAsO), and caesium dialuminium arsenic(V) hexa-kis-[hydrogenarsenate(V)], CsAlAs(HAsO), were solved by single-crystal X-ray diffraction. The three compounds are isotypic and adopt the structure type of RbAlAs(HAsO) (), which itself represents a modification of the RbFe(HPO) structure type and consists of a tetra-hedral-octa-hedral framework in which the slightly disordered cations are located in channels. The three new compounds contain AsO octa-hedra assuming the topological role of O octa-hedra.
View Article and Find Full Text PDFChemistry
October 2018
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of, the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an, 710069, P. R. China.
Whereas the chemistry of single-bond activation by compounds of the main group elements has undergone some development in recent years, the cleavage of multiple bonds remains underexplored. Herein, the reactions of two digallanes bearing α-diimine ligands, namely, [L Ga-GaL ] (1, L =dpp-dad=[(2,6-iPr C H )NC(CH )] ) and [L Ga-GaL ] (2, L =dpp-bian=1,2-[(2,6-iPr C H )NC] C H ), with isothiocyanates are reported. Reactions of 1 or 2 with isothiocyanates in 1:2 molar ratio proceeded with [2+4] cycloaddition of the C=S bond across the C N Ga metallacycle with formation of C-C and S-Ga single bonds to afford [L (RN=C-S)Ga-Ga(S-C=NR)L ] (3, R=Me; 4, R=Ph) and [L (RN=C-S)Ga-Ga(S-C=NR)L ] (8, R=allyl; 9, R=Ph).
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!