2,6-Diphenylphenyl-Based Organometallic Compounds of Gallium

Abstract

(2,6-Diphenylphenyl)lithium−bis(diethyl ether), Ph2C6H3Li·2Et2O (I), was synthesized by reaction of n-butyllithium with 2,6-diphenyl-1-iodobenzene in diethyl ether. Reaction of I with group 13 metal halides, MX3 (M = Ga, X = Cl, I; M = In, X = Cl), affords bis(2,6-diphenylphenyl)gallium iodide, (Ph2C6H3)2GaI (II), bis(2,6-diphenylphenyl)indium chloride, (Ph2C6H3)2InCl (III), and bis(diethyl ether)lithium trichloro-2,6-diphenylphenylgallate, [Li·2Et2O][Ph2C6H3GaCl3] (IV). Reaction of (2,4,6-triphenylphenyl)lithium with GaCl3 gives (diethyl ether)lithium trichloro(2,4,6-triphenylphenyl)gallate, [Li·Et2O][Ph3C6H2GaCl3] (V). The group 13 metal aryls were characterized by 1H and 13C NMR spectroscopy, elemental analyses, and single-crystal X-ray diffraction. The neutral lithium aryl (I) and arylgallium halide species (II) exhibit trigonal-planar coordination, while the coordination of the gallium atoms in anions IV and V assume distorted-tetrahedral conformations.

7Li Solid-state NMR spectroscopic study of aryllithium complexes: effects of aggregation and solvation

“…from an amine to an ether, a change in value is expected, in accord with the observations made previously for the CpLi complexes. The diethyl ether (DEE) complexes of 2,6-diphenylphenyllithium 13 and 2,4,6-triphenylphenyllithium 14 (5 and 4, respectively) are both LiAS 2 systems, with the lithium cation tricoordinated. These two complexes have values of 310 and 308 kHz, respectively.…”

“…13 C. If it can be assumed that there are no fast dynamic processes present, i.e. exchanges, and that the rearrangement of the q zz and 13 C-1 H internuclear vectors are exactly the same, the QSC value is given by the equation 9a QSC D 70.0[T 1 13 C /T 1 7 Li ] 1/2 2 QSC values of some phenyllithium complexes have been reported previously and it was found that this parameter could be used to deduce the aggregation state of these complexes in solution.…”

Gallium: Organometallic ChemistryBased in part on the article Gallium: Organometallic Chemistry by Andrew R. Barron which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

“…The solid-state structure of bis(2,6-diphenylphenyl)gallium iodide, (2,6-Ph 2 C 6 H 3 ) 2 GaI, 16 displays the gallium atom in a somewhat distorted trigonal planar environment (C-Ga-C: 134.3(3)…”

The Directed Lithiation of Benzenoid Aromatic Systems

“…Whereas for R ϭ mesityl (16) [38] the structure is based on a normal (CLi) 2 core, for the more sterically congested ligand in which R ϭ 2,6-(iPr) 2 C 6 H 4 (17) dimerisation occurs by the η 6 -interaction of one R group on each ligand with the metal component of an adjacent monomer. [39] Solvated analogues exhibit even more diverse behaviour; 2,6-(C 10 H 7 ) 2 C 6 H 3 Li·2THF (18), [40] 2,6-Ph 2 C 6 H 3 Li·2OEt 2 (19), [41] 2,6-[4-(tBu)C 6 H 4 ] 2 C 6 H 3 Li·2OEt 2 (20), [42] 2,6-(4-MeOC 6 H 4 ) 2 C 6 H 3 Li·2OEt 2 (21) (wherein the methoxy groups are passive with respect to the metal), [43] 2,6-[2,4,6-(iPr) 3 C 6 H 2 ]C 6 H 3 Li·L (L ϭ OEt 2 22, [44] η 6 -C 6 H 6 23 [39] ) and 2,4,6-Ph 3 C 6 H 2 Li·2OEt 2 (24) [45] are monomers in the solid state while 2,4,6-(iPr) 3 C 6 H 2 Li·OEt 2 (25) [46] and 2,4,6-Me 3 C 6 H 2 Li·2THF (26) [47] form differently solvated dimers. The complex 2,4,6-Ph 3 structure straddle the formal charge centres, one is mono-THF solvated and the other is bis(η 2 -Ph) supported.…”

“…15) [37] to yield µ 2 -biphenyl sulfide-C2,C2, C2Ј,C2Ј-bis(lithium-TMEDA) (40). [56] In the context of ''SϩO class'' directing agents, 3-fluorophenyl(phenyl)sulfone has been shown to undergo lithiation on the fluorinated ring between the two substituents to afford 3-FC 6 H 3 (Li·PMDETA-2)SO 2 Ph (41). [57] Of the two possible coordinating substituents, it is the SO 2 moiety that dominates, with one of its two oxygen centres interacting with the metal [LiϪO ϭ 2.170(8) Å ; Li···F ϭ 3.672(7) Å ].…”