Halide Abstraction as a Route to Cationic Transition-Metal Complexes Containing Two-Coordinate Gallium and Indium Ligand Systems

Abstract

Halide abstraction chemistry offers a viable synthetic route to the cationic two-coordinate complexes [{Cp*Fe(CO) 2 } 2 (µ-E)] + (7, E ) Ga; 8, E ) In) featuring linear bridging gallium or indium atoms. Structural, spectroscopic, and computational studies undertaken on 7 are consistent with appreciable Fe-Ga π-bonding character; in contrast, the indium-bridged complex 8 is shown to feature a much smaller π component to the metal-ligand interaction. Analogous reactions utilizing the supermesityl-substituted gallyl or indyl precursors of the type (η 5 -C 5 R 5 )Fe(CO) 2 E(Mes*)X, on the other hand, lead to the synthesis of halide-bridged species of the type [{(η 5 -C 5 R 5 )Fe(CO) 2 E(Mes*)} 2 (µ-X)] + , presumably by trapping of the highly electrophilic putative cationic diyl complex [(η 5 -C 5 R 5 )Fe(CO) 2 E(Mes*)] + .

Reductive Activation oftripodMetal Compounds: Preparative Application

“…All the compounds containing a linear M–S–M entity so far described (Table 4) have in common that the valence electron count of the [L n MSML n ] m + species corresponds to 36 electrons; the L n M fragments in these compounds are 15 electron species throughout (Table 4). The principle that the 36 electron count of a linear M–E–M entity appears to be a precondition for its formation is further exemplified by the existence of a series of compounds containing a linear L n MEL n M framework with E ranging from main group III (Ga,14a In,14b Tl14c) over main group IV (Ge,15a–15c Sn,15c Pb15d,15e) to main group V (P,16a As,16b–16d Sb16b,16e). The L n M entities are organometallic throughout in all these cases.…”

Periodic Trends in the Binding of a Phosphine‐Tethered Ketone Ligand to Fe, Co, Ni, and Cu

“…The abstraction of ah alide ligand is ac ommon strategyt o induce binding of ah emilabile moiety, [22][23][24][25] as was recently demonstrated by Iluc fort he central olefin of diphosphine-substituted trans-stilbenel igands. [23] To probe whether coordination of the C=Om oiety could be facilitated in the same way, we investigated halide abstraction from the nickel complex ( Ph dpbp)NiCl 2 (4).…”

Reactive p-block cations stabilized by weakly coordinating anions

“…, the [InPt(PPh 3 ) 3 ] + complex with a “naked” Pt-substituted indium cation 179 , 180 as well as the di- and tricoordinate [(FP*) 2 In] + and [(FP*) 2 In(THF)] + complexes. 195 Reacting the chelating phen ligand with the [In(C 6 H 5 F) 2 ] + complex in the presence of silver salt, Krossing et al isolated the silver bound indium dication 17 [(phen) 2 In–Ag(η 3 -C 6 H 5 F)] 2+ that is related to the [InPt(PPh 3 ) 3 ] + complex. 179 , 180 In this complex the tetragonal-pyramidal [In(phen) 2 ] + cation reacts as a Lewis basic donor ( cf.…”