Synthesis, Characterization, and X-ray Crystal Structure of a Gallium Monohydroxide and a Hetero-bimetallic Gallium Zirconium Oxide

Abstract

A monomeric hydroxide of gallium, LGa(Me)OH, containing terminal hydroxide and methyl groups was prepared by the hydrolysis of LGa(Me)Cl in the presence of N-heterocyclic carbene and water [L = HC{(CMe)(2,6-i-Pr2C6H3N)}2] in high yield and in a pure form. LGa(Me)OH was used as a synthon to assemble the first hetero-bimetallic compound with a Ga-O-Zr core, [(LGaMe)(Cp2ZrMe)](mu-O).

β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

“…As reported elsewhere, lithium salts of primary amines are highly reactive and unstable if not stabilized by a base such as N,N,NЈ,NЈ-tetramethylethylenediamine. [18][19][20] Only the hexameric salt (tBuNHLi) 6 has been reported to be stable without any coordinating base. [18] Therefore, the in situ preparation of a known amount of the amine salt was accomplished by slow addition of an excess amount of the corresponding amine to a solution of a known amount of MeLi or nBuLi in THF at -78°C.…”

“…1.805 Å, only bonds without disorder), [24] [24] and LGa(OH) 2 [1.777(1)-1.820(1) Å], [8] but shorter than those in (iPrO)Ga(S 2 CNEt 2 ) 2 [1.932(1) Å] [33] and in LGa(µ-O) 2 -GaL [1.848(1) and 1.854(1) Å]. [9] Furthermore, the Ga-Cl bond lengths found for 5 [2.200 (1) [11] In all nine compounds, the coordination sphere around the central metal has a distorted tetrahedral geometry, where the N endo -M-N endo (1)(2)(3)(4)(5)(6) Table 1.…”

“…From this point of view, only Ga-N bonds fulfil these requirements on stability and reactivity, because the hydrolysis of a Ga-Me moiety is rather difficult and LGaMe(OH) has been reported to melt without decomposition at 200°C. [6] To date, only few such compounds have been reported, and in all cases, their preparation is tedious and/or requires expensive reagents such as Arduengo's imidazoyl carbene [7] [in the case of LGa(NH 2 ) 2 ] [8] or compounds containing the gallium atom in an oxidation state of +I. [9,10] Our aim was to [a] 8) and LGa(OEt)Cl (9), respectively.…”

Oxidative Addition Reactions of Element–Hydrogen Bonds with Different Polarities to a Gallium(I) Compound

“…This is due to the more electronegative oxygen atom compared to tin. The gallium-oxygen bond (d GaO = 179.2(3) pm) is in the normal range for this type of bond; for example, in [LGaMe(OH)] [42] (d GaO = 183.1(1) pm), [LGaH(OH)] [19] (d GaO = 182.0(5) pm), and [LGa(OH) 2 ] [29] (d GaO = 177.7, 182.0 pm) similar distances are observed. The GaN 2 C 3 ring is flatter than that in 2; the gallium atom resides only 36 pm above the N 2 C 3 plane.…”

New route to alkylaluminum hydroxides via hydrolysis of cyclopentadienylaluminum complexes

“…These compounds were found to be stable at ambient conditions and successfully applied as precursors for heterobimetallic species and alumoxanes [10][11][12]. The reaction of (L)AlCl 2 or (L)Al(I)Cl with stoichiometric amounts of water in the presence of N-heterocyclic carbene was previously used for preparation of aluminum hydroxides such as (L)Al(OH) 2 and [(L)Al-(l-OH)Cl] 2 [13][14][15]. These very sophisticated and complicated procedures cause that the synthesis of hydroxyaluminum compounds still is considered as a challenge.…”