Univalent gallium complexes of simple and ansa-arene ligands: effects on the polymerization of isobutylene.

Using Ga(C6 H5 F)2 Al(OR(F))4 (1) (R(F) =C(CF3)3) as starting material, we isolated bis- and tris-η(6) -coordinated gallium(I) arene complex salts of p-xylene (1,4-Me2 C6 H4), hexamethylbenzene (C6 Me6 ), diphenylethane (PhC2 H4 Ph), and m-terphenyl (1,3-Ph2 C6 H4): Ga(1,4-Me2 C6 H4 )2.5 (2(+)), Ga(C6 Me6 )2 (3(+)), Ga(PhC2 H4 Ph) (4(+)) and (C6 H5 F)Ga(μ-1,3-Ph2 C6 H4)2 Ga(C6 H5 F) (5(2+)). 4(+) is the first structurally characterized ansa-like bent sandwich chelate of univalent gallium and 5(2+) the first binuclear gallium(I) complex without a Ga-Ga bond. Beyond confirming the structural findings by multinuclear NMR spectroscopic investigations and density functional calculations (RI-BP86/SV(P) level), Ga(PhC2 H4 Ph) Al(OR(F))4 (4) and (C6 H5 F)Ga(μ-1,3-Ph2 C6 H4)2 Ga(C6 H5 F) {[Al(OR(F) )4] (-)}2 (5), featuring ansa-arene ligands, were tested as catalysts for the synthesis of highly reactive polyisobutylene (HR-PIB). In comparison to the recently published 1 and the Ga(1,3,5-Me3 C6 H3)2 Al(OR(F))4 salt (6) (1,3,5-Me3 C6 H3 =mesitylene), 4 and 5 gave slightly reduced reactivities. This allowed for favorably increased polymerization temperatures of up to +15 °C, while yielding HR-PIB with high contents of terminal olefinic double bonds (α-contents=84-93 %), low molecular weights (Mn =1000-3000 g mol(-1)) and good monomer conversions (up to 83 % in two hours). While the chelate complexes delivered more favorable results than 1 and 6, the reaction kinetics resembled and thus concurred with the recently proposed coordinative polymerization mechanism.