317322-17-1

Upstream product

• 7440-55-3 gallium 
• 223414-22-0 Li(2,6-iPr₂C₆H₃)NC(Me)CHC(Me)N(2,6-iPr₂C₆H₃) 
• 7553-56-2 iodine 
• 210832-39-6 N,N′-bis(2,6-diisopropylphenyl)pentane-2,4-diimine 
• 141556-40-3 1,3,4,5-Tetramethylimidazol-2-yliden 
• 882530-05-4 [Ga₂C₅Me₅][B(C₆H₃(CF₃)2)4]*fluorobenzene 
• 334719-92-5 Dipp₂nacnacLi*Et₂O 

Downstream Products

• 958652-02-3 ZnCl(tetrahydrofuran)2(GaCl(2-[(2,6-diisopropylphenyl)amino]-4-[(2,6-diisopropylphenyl)imino]-2-pentene)) 
• 1243809-81-5 [Ga(CH[CMeN(2,6-iPr₂C₆H₃)]₂)(η²-P₄)] 

Relevant academic research and scientific papers

Addressing the chemical sorcery of "GaI": Benefits of solid-state analysis aiding in the synthesis of P→Ga coordination compounds

The differing structures and reactivities of "GaI" samples prepared with different reaction times have been investigated in detail. Analysis by FT-Raman spectroscopy, powder X-ray diffraction, 71Ga solid-state NMR spectroscopy, and 127I nuclear quadrupole

Synthesis of Heterobimetallic Group 13 Compounds via Oxidative Addition Reaction of Gallanediyl LGa and InEt3

Equimolar amounts of LGa (L = [(2,6-i-Pr2-C6H3)NC(Me)]2CH) and InEt3 were found to react with insertion into the In-carbon bond and formation of LGa(Et)InEt2 (1), while in the presence of the N-heterocyclic carbene It-Bu [C(Nt-Bu2CH)2], the base-stabilized compound LGa(Et)Et2In←It-Bu (2) was formed, which shows an abnormal binding mode of the NHC group. In addition, the reaction of InEt3 with two equivalents of LGa occurred with double insertion and formation of [LGa(Et)]2InEt (3). 1-3 were characterized by heteronuclear NMR (1H, 13C) and IR spectroscopy, their solid-state structures were determined by single-crystal X-ray analyses, and their thermal stability was investigated by in situ NMR spectroscopy. (Chemical Equation Presented).

Reductive elimination of [AlH2]+from a cationic Ga-Al dihydride

Oxidative addition of TMEDA-supported [AlH2]+to [{BDI}Ga] (BDI = {HC(C(CH3)N(2,6-iPr2-C6H3))2}) provides [{BDI}Ga(H)-Al(H)(tmeda)][B(C6H3-3,5-Me2)4] (TMEDA =N,N,N′N′-tetramethylethylenediamine) with a covalent metal-metal bond. The reaction is readily reversed by substituting TMEDA for an N-heterocyclic carbene or dissolving in THF.

Salt metathesis as an alternative approach to access aluminium(i) and gallium(i) ?-diketiminates

Salt metathesis,i.e.the reaction of sodium ?-diketiminate with (AlCp*)4and GaCp*, respectively, is a valuable pathway to access the respective aluminium(i) and gallium(i) ?-diketiminatesIandII. The protocol gives better yields compared to the established procedures and avoids the use of strong reducing agents such as metallic potassium. Furthermore, the aluminium(i) ?-diketiminateIwas found to react with itself and yields upon C-N bond cleavage and hydrogen-atom transfer the asymmetric dinuclear aluminium(iii) complexVthat is readily separated fromIby crystallisation. The reaction mechanism has been probed by means of DFT and DLPNO-CCSD(T) calculations and the computational findings are in good agreement with the experimental observations.

A silicon–carbonyl complex stable at room temperature

Main-group-element compounds with energetically high-lying donor and low-lying acceptor orbitals are able to mimic chemical bonding motifs and reactivity patterns known in transition metal chemistry, including small-molecule activation and catalytic reactions. Monovalent group 13 compounds and divalent group 14 compounds, particularly silylenes, have been shown to be excellent candidates for this purpose. However, one of the most common reactions of transition metal complexes, the direct reaction with carbon monoxide and formation of room-temperature isolable carbonyl complexes, is virtually unknown in main-group-element chemistry. Here, we show the synthesis, single-crystal X-ray structure, and density functional theory computations of a room-temperature-stable silylene carbonyl complex [L(Br)Ga]2Si:–CO (L = HC[C(Me)N(2,6-iPr2-C6H3)]2), which was obtained by direct carbonylation of the electron-rich silylene intermediate [L(Br)Ga]2Si:. Furthermore, [L(Br)Ga]2Si:–CO reacts with H2 and PBr3 with bond activation, whereas the reaction with cyclohexyl isocyanide proceeds with CO substitution. [Figure not available: see fulltext.]

Comprehensive Study on Reactions of Group 13 Diyls with Tetraorganodipentelanes

L1Ga {L1 = HC[C(Me)N(2,6-iPr2C6H3)]2} reversibly reacts with E2Ph4 (E = Sb, Bi) in a temperature-dependent equilibrium reaction with insertion into the E-E bond and formation of L1Ga(EPh2)2 (E = Sb 1, Bi 2). Analogous findings were observed in the reactions of L2Ga {L2 = (C6H11)2NC[N(2,6-iPr2C6H3)]2} with E2R4 (R = Ph, Et), yielding L2Ga(EPh2)2 (E = Sb 3, Bi 4) and L2Ga(EEt2)2 (E = Sb 5, Bi 6). 1-3 and 5 were isolated by fractional crystallization at low temperature, whereas 4 and 6 could not be isolated in their pure form even at low temperature. In contrast, reactions of [Cp?Al]4 (Cp? = C5Me5) with Sb2R4 (R = Ph, Et) and Bi2Et4 did not proceed with insertion into the E-E bonds but with formation of (Cp?Al)3E2 (E = Sb, 7; Bi, 8), whereas the reaction with Bi2Ph4 yielded metallic bismuth. 8 was also formed in the reaction of [Cp?Al]4 and BiEt3 at ambient temperature, whereas the analogous reaction of [Cp?Al]4 with SbEt3 did not yield 7 even under drastic reaction conditions (120 °C, 3 days). In contrast, Cp?Ga and Sb2R4 (R = Ph, Et) were found to react only at elevated temperature (120 °C) with formation of antimony metal.

The [Ga2(C5Me5)]+ ion: Bipyramidal double-cone structure and weakly coordinated, monovalent Ga +

(Figure Presented) Partial protolysis of GaCp* with [H-(OEt 2)2]+[BArF]- afforded the GaI compound [Ga2Cp*]+[BAr F]- (see structure). Experimental and computational studies confirm the mainly ionic structure of the cation, in which the Ga + ions are only weakly covalently stabilized by a bridging Cp* ligand. Initial experiments point to the interesting synthetic potential of this compound as a source for Ga+ in solution.

Synthesis and characterization of HC{C(Me)N(C6H3-2,6-i-Pr2)}2 MX2 (M = Al, X = Cl, I; M = Ga, In, X = Me, Cl, I): Sterically encumbered β-diketiminate group 13 metal derivatives

A series of group 13 metal complexes featuring the β-diketiminate ligand [{(C6H3-2,6-i-Pr2)NC(Me)}2CH] - (i.e., [Dipp2nacnac]-, Dipp = C6H3-2,6-i-Pr2) have been prepared and spectroscopically and structurally characterized. The chloride derivatives Dipp2nacnacMCl2 (M = Al (3), Ga (5), In (8)) were isolated in good yield by the reaction of 1 equiv of Dipp2nacnacLi·Et2O (2) and the respective metal halides. The iodide derivatives Dipp2nacnacMl2 (M = Al (4), Ga (6), In (9)), which are useful for reduction to afford M(I) species, were made by a variety of routes. Thus, 4 was obtained by treatment of the previously reported Dipp2nacnacAlMe2 with I2, whereas the gallium analogue 6 was obtained as a product of the reaction of GaI with Dipp2nacnacLi·EtzO, and 9 was obtained by direct reaction of InI3 and the lithium salt. The methyl derivatives Dipp2nacnacMMe2 (M = Ga (7), In (10)), which are analogous to the previously reported Dipp2nacnacAlMe2, were synthesized by the reaction of GaMe3 with Dipp2nacnacH (1) or by reaction of the indium chloride derivative 8 with 2 equiv of MeMgBr in diethyl ether. The compounds 3-10 exist as colorless, air- and moisture-sensitive crystalline solids. Their X-ray crystal structures feature nearly planar C3N2 arrays in the Dipp2nacnac ligand backbone with short C-C and C-N distances that are consistent with a delocalized structure. However, there are large dihedral angles between the C3N2 plane and the N2M metal coordination plane which have been attributed mainly to steric effects. The relatively short M-N distances are consistent with the coordination numbers of the metals and the normal/dative character of the nitrogen ligands. The compounds were also characterized by 1H and 13C NMR spectroscopy. 1H NMR data for 7 revealed equivalent methyl groups whereas the spectrum of 10 displayed two In-Me signals which indicated that ring wagging was slow on the 1H NMR time scale.