Experimental Confirmation of an Iron−Gallium Multiple Bond:  Synthesis, Structure, and Bonding of a Ferrogallyne

Abstract

Reaction of disodium tetracarbonylferrate, Na2[Fe(CO)4], with [2,6-bis(2,4,6-triisopropylphenyl)phenyl]gallium dichloride, (Mes*2C6H3)GaCl2 (Mes* = 2,4,6-triisopropylphenyl), affords tetracarbonyliron [2,6-bis(2,4,6-triisopropylphenyl)phenyl]gallyne, (CO)4Fe⋮Ga(C6H3Mes*2), as anaerobically stable yellow prism crystals. The title compound offers evidence in support of an iron−gallium triple bondthe first ferrogallyne.

Synthesis of the Sterically Related Nickel Gallanediyl Complexes [Ni(CO)3(GaAr′)] (Ar′ = C6H3-2,6-(C6H3-2,6-iPr2)2) and [Ni(CO)3(GaL)] (L = HC[C(CH3)N(C6H3-2,6-iPr2)]2): Thermal Decomposition of [Ni(CO)3(GaAr′)] to give the Cluster [Ni4(CO)7(GaAr′)3]

“…We have shown that low coordination Ga(I) species containing bulky aryl ligands Ar 0 GaGaAr 0 (Ar 0 = C 6 H 3 -2,6-(Dipp) 2 ) or GaL (L = HC[C(Me)N(Dipp)] 2 , Dipp = 2,6-iPr 2 C 6 H 3 ) are monomeric in solution and exhibit Lewis base behavior toward iron carbonyl to give monomeric Ar 0 GaFe(CO) 4 or LGaFe(CO) 4 complexes [25][26][27]. Similar to those previously reported for RMFe(CO) 4 (M = Al, R = g 5 -C 5 Me 5 (Cp*) [For reviews of MR complexes of ligands: [28][29][30][31][32]; M = Ga, R = C 6 H 3 -2,6-(2,4,6-iPr 3 C 6 H 2 ) 2 [33]). In this context we were interested in studying the reactivity of Ar 0 GaGaAr 0 or GaL with Ni(CO) 4 .…”

Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals

“…Two more recent examples are the FeÀGe and FeÀGa complexes [{Cp*(CO) 2 FeÀGeMe 2 (dmap) }] (dmap 4-dimethylaminopyridine) [13] and [(CO) 4 FeÀGaAr*] (Ar* 2,6-bis(2,4,6-triisopropylphenyl)phenyl). [14] et al on inidene complexes [22] and by Herrmann et al on complexes and metal cumulenes with substituent-free main group elements, [23] and has been covered in a series of review articles and monographies.…”

“…[76] [77] which represents a first example of the existence of complexes that are homoleptic with regard to an earth metal as ligator. This example and the complexes [{CpNiAlCp*} 2 ], [78] [Cp*AlÀFe-(CO) 4 ], [79] and[(CO) 4 FeÀGaAr*] (Ar* 2,6-bis(2,4,6-triisopropylphenyl)phenyl] [14] indicate the lively development and the current trends in this field.…”

Reactions of Terphenyl-Substituted Digallene AriPr4GaGaAriPr4 (AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) with Transition Metal Carbonyls and Theoretical Investigation of the Mechanism of Addition

“…1 H NMR, 13 C NMR, FT-IR and UV-Vis spectra of compounds 1-3 and 5, 1 H NMR, 13 C NMR and UV-Vis spectra for 4.…”