TY - JOUR
T1 - Bimetallic complexes for enhancing catalyst efficiency
T2 - Probing the relationship between activity and intermetallic distance
AU - Timerbulatova, Marina G.
AU - Gatus, Mark R.D.
AU - Vuong, Khuong Q.
AU - Bhadbhade, Mohan
AU - Algarra, Andrés G.
AU - Macgregor, Stuart A.
AU - Messerle, Barbara A.
PY - 2013/9/23
Y1 - 2013/9/23
N2 - A series of new homoditopic ligands (14-17) containing two bis(pyrazol-1-yl)methane moieties connected to either flexible (1,6-bis(bis(pyrazol-1-yl)methyl)hexane, L6C (14); 1,7-bis(bis(pyrazol-1-yl)methyl)heptane, L7C (15)) or rigid scaffolds (4,5-bis(bis(pyrazol-1-yl)methyl)-9,9-dimethylxanthene, LXan (16); 4,6-bis(bis(pyrazol-1-yl)methyl)dibenzofuran, LDib (17)) were synthesized. A series of bimetallic rhodium(I) complexes [Rh2(CO) 4(LX)][BArF4]2 (X = Xan (8), Dib (9), Fc ((1,1′-bis(bis(pyrazol-1-yl)methyl)ferrocene) (10)), 6C (11), 7C (12)) and [Rh2(COD)2(LX)][BAr F4]2 (COD = 1,5-cyclooctadiene, X = 6C (21), 7C (22)) as well as the monometallic complexes [Rh(CO)2(L Ph)][BArF4] (7, LPh = α,α-bis(pyrazol-1-yl)toluene) and [Rh(COD)(LPh)][BAr F4] (20) were synthesized. The solid-state structures of 8, 10, 16, 17, and 21 were determined using single-crystal X-ray diffraction analysis. The catalytic activity of complexes 7-12 was established for the dihydroalkoxylation of the alkynediols 2-(5-hydroxypent-1-ynyl)benzyl alcohol (I) and 2-(4-hydroxybut-1-ynyl)benzyl alcohol (II). The rigid bimetallic scaffolds LXan and LDib were found to yield the most active catalysts, 8 and 9, respectively, with 9 achieving a reaction rate 5-6 times faster than the monometallic complex 7 for the dihydroalkoxylation of I. Density functional theory calculations were used to examine the intermetallic Rh···Rh distances in 8 and 9, and these were compared with those of three other related bimetallic catalysts reported previously. The calculations showed all these species to be very flexible at minimal energetic cost, both in terms of the Rh···Rh distance and in being able to access a range of different conformations. No clear correlation between Rh···Rh distance and catalytic activity was established here, which suggests that the observed experimental correlation between catalyst structure and activity may derive from the structures of key reaction intermediates.
AB - A series of new homoditopic ligands (14-17) containing two bis(pyrazol-1-yl)methane moieties connected to either flexible (1,6-bis(bis(pyrazol-1-yl)methyl)hexane, L6C (14); 1,7-bis(bis(pyrazol-1-yl)methyl)heptane, L7C (15)) or rigid scaffolds (4,5-bis(bis(pyrazol-1-yl)methyl)-9,9-dimethylxanthene, LXan (16); 4,6-bis(bis(pyrazol-1-yl)methyl)dibenzofuran, LDib (17)) were synthesized. A series of bimetallic rhodium(I) complexes [Rh2(CO) 4(LX)][BArF4]2 (X = Xan (8), Dib (9), Fc ((1,1′-bis(bis(pyrazol-1-yl)methyl)ferrocene) (10)), 6C (11), 7C (12)) and [Rh2(COD)2(LX)][BAr F4]2 (COD = 1,5-cyclooctadiene, X = 6C (21), 7C (22)) as well as the monometallic complexes [Rh(CO)2(L Ph)][BArF4] (7, LPh = α,α-bis(pyrazol-1-yl)toluene) and [Rh(COD)(LPh)][BAr F4] (20) were synthesized. The solid-state structures of 8, 10, 16, 17, and 21 were determined using single-crystal X-ray diffraction analysis. The catalytic activity of complexes 7-12 was established for the dihydroalkoxylation of the alkynediols 2-(5-hydroxypent-1-ynyl)benzyl alcohol (I) and 2-(4-hydroxybut-1-ynyl)benzyl alcohol (II). The rigid bimetallic scaffolds LXan and LDib were found to yield the most active catalysts, 8 and 9, respectively, with 9 achieving a reaction rate 5-6 times faster than the monometallic complex 7 for the dihydroalkoxylation of I. Density functional theory calculations were used to examine the intermetallic Rh···Rh distances in 8 and 9, and these were compared with those of three other related bimetallic catalysts reported previously. The calculations showed all these species to be very flexible at minimal energetic cost, both in terms of the Rh···Rh distance and in being able to access a range of different conformations. No clear correlation between Rh···Rh distance and catalytic activity was established here, which suggests that the observed experimental correlation between catalyst structure and activity may derive from the structures of key reaction intermediates.
UR - http://www.scopus.com/inward/record.url?scp=84884638555&partnerID=8YFLogxK
U2 - 10.1021/om4005059
DO - 10.1021/om4005059
M3 - Article
AN - SCOPUS:84884638555
SN - 0276-7333
VL - 32
SP - 5071
EP - 5081
JO - Organometallics
JF - Organometallics
IS - 18
ER -