TY - JOUR
T1 - Rhenium hydride/boron lewis acid cocatalysis of alkene hydrogenations
T2 - Activities comparable to those of precious metal systems
AU - Jiang, Yanfeng
AU - Hess, Jeannine
AU - Fox, Thomas
AU - Berke, Heinz
PY - 2010/12/29
Y1 - 2010/12/29
N2 - Dibromonitrosyl(dihydrogen)rhenium(I) complexes [ReBr2(NO) (PR3)2(η2-H2)] (1; R = iPr, a; Cy, b) and Me2NH•BH3 (DMAB) catalyze at either 90 °C or ambient temperature under 10 bar of H2 the hydrogenation of various terminal and cyclic alkenes (1-hexene, 1-octene, cyclooctene, styrene, 1,5-cyclooctadiene, 1,7-octadiene, α-methylstyrene). Maximum turnover frequency (TOF) values of 3.6 × 104 h-1 at 90 °C and 1.7 × 104 h-1 at 23 °C were achieved in the hydrogenation of 1-hexene. The extraordinary catalytic performance of the 1/DMAB system is attributed to the formation of five-coordinate rhenium(I) hydride complexes [Re(Br)(H)(NO)(PR3)2] (2; R = iPr, a; Cy, b) and the action of the Lewis acid BH3 originating from DMAB. The related 2/BH3•THF catalytic system also exhibits under the same conditions high activity in the hydrogenation of various alkenes with a maximum turnover number (TON) of 1.2 × 104 and a maximum TOF of 4.0 × 104 h-1. For the hydrogenations of 1-hexene with 2a and 2b, the effect of the strength of the boron Lewis acid was studied, the acidity being in the following order: BCl3 > BH3 > BEt3 ≈ BF3 > B(C6F5) 3 > BPh3 ≫ B(OMe)3. The order in catalytic activity was found to be B(C6F5)3 > BEt3 ≈ BH3•THF > BPh3 ≫ BF3•OEt2 > B(OMe)3 ≫ BCl 3. The stability of the catalytic systems was checked via TON vs time plots, which revealed the boron Lewis acids to cause an approximate inverse order with the Lewis acid strength: BPh3 > BEt3 ≈ BH3•THF > B(C6F5)3. For the 2a/BPh3 system a maximum TON of 3.1 × 104 and for the 2a/B(C6F5)3 system a maximum TOF of 5.6 × 104 h-1 were obtained in the hydrogenation of 1-hexene. On the basis of kinetic isotope effect determinations, H 2/D2 scrambling, halide exchange experiments, Lewis acid variations, and isomerization of terminal alkenes, an Osborn-type catalytic cycle is proposed with olefin before H2 addition. The active rhenium(I) monohydride species is assumed to be formed via reversible bromide abstraction with the "cocatalytic" Lewis acid. Homogeneity of the hydrogenations was tested with filtration and mercury poisoning experiments. These "rhenium(I) hydride/boron Lewis acid" systems demonstrate catalytic activities comparable to those of Wilkinson- or Schrock-Osborn-type hydrogenations accomplished with precious metal catalysts.
AB - Dibromonitrosyl(dihydrogen)rhenium(I) complexes [ReBr2(NO) (PR3)2(η2-H2)] (1; R = iPr, a; Cy, b) and Me2NH•BH3 (DMAB) catalyze at either 90 °C or ambient temperature under 10 bar of H2 the hydrogenation of various terminal and cyclic alkenes (1-hexene, 1-octene, cyclooctene, styrene, 1,5-cyclooctadiene, 1,7-octadiene, α-methylstyrene). Maximum turnover frequency (TOF) values of 3.6 × 104 h-1 at 90 °C and 1.7 × 104 h-1 at 23 °C were achieved in the hydrogenation of 1-hexene. The extraordinary catalytic performance of the 1/DMAB system is attributed to the formation of five-coordinate rhenium(I) hydride complexes [Re(Br)(H)(NO)(PR3)2] (2; R = iPr, a; Cy, b) and the action of the Lewis acid BH3 originating from DMAB. The related 2/BH3•THF catalytic system also exhibits under the same conditions high activity in the hydrogenation of various alkenes with a maximum turnover number (TON) of 1.2 × 104 and a maximum TOF of 4.0 × 104 h-1. For the hydrogenations of 1-hexene with 2a and 2b, the effect of the strength of the boron Lewis acid was studied, the acidity being in the following order: BCl3 > BH3 > BEt3 ≈ BF3 > B(C6F5) 3 > BPh3 ≫ B(OMe)3. The order in catalytic activity was found to be B(C6F5)3 > BEt3 ≈ BH3•THF > BPh3 ≫ BF3•OEt2 > B(OMe)3 ≫ BCl 3. The stability of the catalytic systems was checked via TON vs time plots, which revealed the boron Lewis acids to cause an approximate inverse order with the Lewis acid strength: BPh3 > BEt3 ≈ BH3•THF > B(C6F5)3. For the 2a/BPh3 system a maximum TON of 3.1 × 104 and for the 2a/B(C6F5)3 system a maximum TOF of 5.6 × 104 h-1 were obtained in the hydrogenation of 1-hexene. On the basis of kinetic isotope effect determinations, H 2/D2 scrambling, halide exchange experiments, Lewis acid variations, and isomerization of terminal alkenes, an Osborn-type catalytic cycle is proposed with olefin before H2 addition. The active rhenium(I) monohydride species is assumed to be formed via reversible bromide abstraction with the "cocatalytic" Lewis acid. Homogeneity of the hydrogenations was tested with filtration and mercury poisoning experiments. These "rhenium(I) hydride/boron Lewis acid" systems demonstrate catalytic activities comparable to those of Wilkinson- or Schrock-Osborn-type hydrogenations accomplished with precious metal catalysts.
UR - http://www.scopus.com/inward/record.url?scp=78650607214&partnerID=8YFLogxK
U2 - 10.1021/ja107187r
DO - 10.1021/ja107187r
M3 - Article
AN - SCOPUS:78650607214
SN - 0002-7863
VL - 132
SP - 18233
EP - 18247
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 51
ER -
