Chromium, Iron and Cobalt Carbonyl Complexes with Gallium Halides: Synthesis and Structures

Abstract

The reactions of gallium subhalides Ga2X4·2dioxane (X = Cl, Br) and “GaI” with carbonylmetallates of chromium, iron and cobalt result in the formation of various gallium halide complexes. These are [(CO)5CrGaBr(thf)2] (6), with a terminal GaX unit, and [(CO)4FeGaCl(thf)]2 (1), [(CO)4FeGaCl2Na(thf)2]x (2), [(CO)4FeGaI2Na(thf)3]2 (4) and [Cr2(CO)8(GaI2)INa2(thf)7]x (8) with GaX units in the bridging positions of gallium–transition‐metal rings. In addition, mixed cyclic gallium–iron hydroxides [{(CO)4Fe}2Ga4Cl5(OH)3(thf)] 3 and 4 and gallium oxo/hydroxo cages 5, 9 and 10 were observed. Rings of [{GaCo4(CO)14}K(thf)]6 (11), prepared from Ga4Cl4R4 [R = Si(SiMe3)3] and K[Co(CO)4], are connected through isocarbonyl–potassium interactions to form channels. All compounds were characterized spectroscopically and by X‐ray crystallography. DFT calculations were performed on cobalt–gallium complexes to evaluate their bonding properties.

Boron, aluminium, gallium, indium and thallium

“…x , all of which have been structurally characterised using single crystal X-ray diffraction. 285 The neutral trigallane R 3 Ga 3 I 2 has been reportedly obtained in high yields by reaction of ''GaI'' with the sterically demanding lithium N,N 0 -dicyclohexylneopentylamidinate. Its chemical reactions with N-lithio-2-propanimine, sodium superhydride and elemental iodine have been investigated and DFT calculations have been performed to elucidate the bonding situation.…”

Reactivity of Transition Metal Gallylene Complexes Toward Substrates with Multiple Carbon–Element Bonds

“…Gallylenes coordinated to transition metals represent more conventional organometallic Lewis pairs . Usually, stabilization of the gallium atom bearing a free electron pair is achieved by the use of some spacious ligand such as the cyclopentadienyl ligand, − β-diketiminate, − bulky silyl, aryl, , various pincer-type ligands, imino-amido ligands, − boryl, , or butadienyl . Indeed, the LGa ligand can be viewed isolobal/isoelectronic to CO and N 2 . − The structure, stability, and physical properties of LGa species , and their LAl − counterparts became much clearer after the exhausting studies within the last three decades.…”

Photoinduced Formal Gallylene Transfer from Gallium-Bridged Dimetallic Complexes to 16-Electron Metal Fragments

“…Over the past decade, there has been remarkable progress in the investigation of the synthesis and structures of transition-metal complexes with low-valent gallylene ligands RGa. , The isolation of the first base-free terminal gallylene complex Ar*GaFe(CO) 4 (Ar* = 2,6-(2,4,6- i Pr 3 C 6 H 2 ) 2 C 6 H 3 ) stimulated the research in this area. , Recent development of gallylene ligand precursors, such as Cp*Ga (Cp* = η 5 -C 5 Me 5 ), , (Me 3 Si) 3 CGa, , and gallium(I) N-heterocycles, ,,, has facilitated the preparation of gallylene complexes by ligand substitution of labile ligands with the gallylene ligand precursors.…”