Molecular heterogeneous catalysis: a single-site zeolite-supported rhodium complex for acetylene cyclotrimerization.
By anchoring metal complexes to supports, researchers have attempted to combine the high activity and selectivity of molecular homogeneous catalysis with the ease of separation and lack of corrosion of heterogeneous catalysis. However, the intrinsic nonuniformity of supports has limited attempts to make supported catalysts truly uniform. We report the synthesis and performance of such a catalyst, made from [Rh(C(2)H(4))(2)(CH(3)COCHCOCH(3))] and a crystalline support, dealuminated Y zeolite, giving {Rh(C(2)H(4))(2)} groups anchored by bonds to two zeolite oxygen ions, with the structure determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and the uniformity of the supported complex demonstrated by (13)C NMR spectroscopy. When the ethylene ligands are replaced by acetylene, catalytic cyclotrimerization to benzene ensues. Characterizing the working catalyst, we observed evidence of intermediates in the catalytic cycle by NMR spectroscopy. Calculations at the level of density functional theory confirmed the structure of the as-synthesized supported metal complex determined by EXAFS spectroscopy. With this structure as an anchor, we used the computational results to elucidate the catalytic cycle (including transition states), finding results in agreement with the NMR spectra.
Department of Chemistry, University of Southern California, Los Angeles, CA 90089, USA.
Philip W
PW
Kletnieks
Ann J
AJ
Liang
Raluca
R
Craciun
Justin O
JO
Ehresmann
David M
DM
Marcus
Vinesh A
VA
Bhirud
Meghan M
MM
Klaric
Miranda J
MJ
Hayman
Darryl R
DR
Guenther
Olesya P
OP
Bagatchenko
David A
DA
Dixon
Bruce C
BC
Gates
James F
JF
Haw