Aliphatic and aromatic C-H activation of benzo[h] quinolines by Rh(I). Unique precursor dependent formation of mono-, di- and trinuclear complexes

作者：Salem Hiyam; Leitus Gregory; Shimon Linda J W; Diskin Posner Yael; Milstein David^*

来源：Inorganica Chimica Acta, 2011, 369(1): 260-269.

DOI：10.1016/j.ica.2010.12.064

• C-H bond activation
• Rhodium complexes
• 7,8-Benzo[h]quinolone
• 10-Methyl benzo[h]quinolone
• Trinuclear complex

Treatment of 7,8-benzo[h] quinoline (bhq-H, 1) and 10-methyl benzo[h] quinoline (bhq-Me, 3) with [Rh(C2H4)(2)(THF)(2)][BF4] resulted in double C-H activation of aliphatic and aromatic C-H bonds, yielding the Rh(III) complexes 4 and 5, respectively. The structures of 4 and 5 were revealed by X-ray diffraction. The reaction of 1 with two other slightly different rhodium precursors, [Rh(olefin)(n)(THF)(2)][BF4] (COE (n = 2), COD (n = 1)), led to completely different products, a dinuclear complex 7 and a trinuclear complex 6, respectively, which were characterized by X-ray diffraction. Complex 6 exhibits a rare linear Rh-Rh-Rh structure. Utilizing excess of 1 with [Rh(COD)(THF)(2)][BF4] led to the formation of a new product 8 with no C-H bond activation taking place. Additional C-H activation products of 1, cationic and neutral, in the presence of PiPr(3) (9a, 9b and 10) are also presented.

• 出版日期2011-4-15