TY - JOUR
T1 - When is a nanoparticle a cluster? An operando EXAFS study of amine borane dehydrocoupling by Rh4-6 clusters
AU - Fulton, John L.
AU - Linehan, John C.
AU - Autrey, Tom
AU - Balasubramanian, Mahalingam
AU - Chen, Yongsheng
AU - Szymczak, Nathaniel K.
N1 - Copyright:
Copyright 2009 Elsevier B.V., All rights reserved.
PY - 2007/10/3
Y1 - 2007/10/3
N2 - X-ray absorption fine structure (XAFS) is used to determine the structure of the rhodium cluster present during the catalyzed dehydrocoupling of amine boranes under operando conditions. We show how a variety of XAFS strategies can be used in combination with other analytical methods to differentiate homogeneous from heterogeneous systems. Analysis of the in situ XAFS spectra using a series of amine boranes (NH3BH3, R 2NHBH3, and RNH2BH3 where R = methyl, isopropyl, tert-butyl, and cyclohexyl) and rhodium catalyst precursor compounds (including chloro-(1,5-cyclooctadiene)rhodium (I) dimer, bis(1,5-cyclooctadiene)rhodium (I) trifluoromethanesulfonate, chlorodicarbonylrhodium (I) dimer, dichloro(pentamethylcylcopentadienyl)rhodium (III) dimer, hexarhodium hexadecacarbonyl, and tetrarhodium dodecacarbonyl) strongly suggest that the active catalyst species for this reaction is a homogeneous rhodium complex. Rhodium clusters containing four or six rhodium atoms (Rh4-6) bound to amine boranes are observed as the major (>99%) rhodium containing species during and after the catalyzed anaerobic dehydrocoupling. During the later stages of the reaction a nonmetallic rhodium complex precipitates in which individual Rh4-6 clusters likely form polymer chains ligated by the reaction products that have two or more ligating sites. The best fits of the XAFS data, using ab initio calculations of FEFF theory, show that the major rhodium species (80%) has each rhodium atom directly bound to three rhodium atoms with an observed bond distance of 2.73 Å and to two boron atoms at 2.10 Å. A minor (20%) rhodium species has each rhodium atom bound to four rhodium atoms with a bond distance of about 2.73 Å and a single rhodium atom at a nonbonding distance of 3.88 Å. No metallic rhodium was observed at any time during the anaerobic reaction.
AB - X-ray absorption fine structure (XAFS) is used to determine the structure of the rhodium cluster present during the catalyzed dehydrocoupling of amine boranes under operando conditions. We show how a variety of XAFS strategies can be used in combination with other analytical methods to differentiate homogeneous from heterogeneous systems. Analysis of the in situ XAFS spectra using a series of amine boranes (NH3BH3, R 2NHBH3, and RNH2BH3 where R = methyl, isopropyl, tert-butyl, and cyclohexyl) and rhodium catalyst precursor compounds (including chloro-(1,5-cyclooctadiene)rhodium (I) dimer, bis(1,5-cyclooctadiene)rhodium (I) trifluoromethanesulfonate, chlorodicarbonylrhodium (I) dimer, dichloro(pentamethylcylcopentadienyl)rhodium (III) dimer, hexarhodium hexadecacarbonyl, and tetrarhodium dodecacarbonyl) strongly suggest that the active catalyst species for this reaction is a homogeneous rhodium complex. Rhodium clusters containing four or six rhodium atoms (Rh4-6) bound to amine boranes are observed as the major (>99%) rhodium containing species during and after the catalyzed anaerobic dehydrocoupling. During the later stages of the reaction a nonmetallic rhodium complex precipitates in which individual Rh4-6 clusters likely form polymer chains ligated by the reaction products that have two or more ligating sites. The best fits of the XAFS data, using ab initio calculations of FEFF theory, show that the major rhodium species (80%) has each rhodium atom directly bound to three rhodium atoms with an observed bond distance of 2.73 Å and to two boron atoms at 2.10 Å. A minor (20%) rhodium species has each rhodium atom bound to four rhodium atoms with a bond distance of about 2.73 Å and a single rhodium atom at a nonbonding distance of 3.88 Å. No metallic rhodium was observed at any time during the anaerobic reaction.
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U2 - 10.1021/ja073331l
DO - 10.1021/ja073331l
M3 - Article
C2 - 17824610
AN - SCOPUS:34848821938
VL - 129
SP - 11936
EP - 11949
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 39
ER -