TY - JOUR
T1 - Surface Organometallic Chemistry of Tin
T2 - Reaction of Hydridotris(butyl)tin with the Surfaces of Partially Dehydroxylated Aluminas
AU - Nédez, Christophe
AU - Lefebvre, Frédéric
AU - Choplin, Agnès
AU - Niccolai, Gerald P.
AU - Basset, Jean-Marie Maurice
AU - Benazzi, Eric
PY - 1994/9/1
Y1 - 1994/9/1
N2 - Reaction of Bu3SnH with the surface of partially dehydroxylated aluminas was followed by analysis of the evolved gases and infrared, 13C CP-MAS NMR, and 119Sn MAS NMR spectroscopies. At room temperature, the infrared and 13C CP-MAS NMR data suggest an initial interaction of Bu3SnH with the hydroxyl groups of the η-alumina(500) surface via hydrogen-type bonding with the δ-CH3 groups of the butyl ligand. The formation of the grafted entity >AlOSnBu3 was accompanied by the release of 1 mol H2 per mole of Sn. Data were obtained on α-, γ-, and η-aluminas dehydroxylated at either 200 or 500 °C. The various NMR data coupled with published data for molecular analogs indicate that the tin atoms can be tetra- or pentacoordinated on the alumina surface. 27Al NMR is used to estimate the ratio of octahedral to tetrahedral aluminum atoms in various aluminas. Detailed study of the 119Sn NMR of the series of Sn/Al2O3 species revealed three basic types of tin coordination environments. Tin signals around 80 ppm present in some of the complexes are attributed to >Al0SnBu3 or tetracoordinated tin. Peaks in the regions around -230 and -170 ppm are ascribed to a pentacoordinated tris(alkyl)tin fragment. The fifth ligand coordinated to tin may be either a hydroxyl group or a surface O2- ion: formation of (> Al0)(> Al0H)Sn(n-C4H9)3 and of (>AlO)-(>AlO2~)Sn(n-C4H9)3. The complexity of these resonances and the dependence thereof on the type of alumina used and the degree of dehydroxylation are attributed to the influence of the geometry of neighboring aluminum atoms on the tin chemical shift. These results apply the extreme sensitivity of tin chemical shifts to molecular enviroment, producing a method whereby surface organometallic complexes of tin can be used as molecular probes for determining surface structures of oxides. The 119Sn NMR is shown to be much more sensitive than other previously used spectroscopic techniques, such as IR, Raman, and 29Al NMR.
AB - Reaction of Bu3SnH with the surface of partially dehydroxylated aluminas was followed by analysis of the evolved gases and infrared, 13C CP-MAS NMR, and 119Sn MAS NMR spectroscopies. At room temperature, the infrared and 13C CP-MAS NMR data suggest an initial interaction of Bu3SnH with the hydroxyl groups of the η-alumina(500) surface via hydrogen-type bonding with the δ-CH3 groups of the butyl ligand. The formation of the grafted entity >AlOSnBu3 was accompanied by the release of 1 mol H2 per mole of Sn. Data were obtained on α-, γ-, and η-aluminas dehydroxylated at either 200 or 500 °C. The various NMR data coupled with published data for molecular analogs indicate that the tin atoms can be tetra- or pentacoordinated on the alumina surface. 27Al NMR is used to estimate the ratio of octahedral to tetrahedral aluminum atoms in various aluminas. Detailed study of the 119Sn NMR of the series of Sn/Al2O3 species revealed three basic types of tin coordination environments. Tin signals around 80 ppm present in some of the complexes are attributed to >Al0SnBu3 or tetracoordinated tin. Peaks in the regions around -230 and -170 ppm are ascribed to a pentacoordinated tris(alkyl)tin fragment. The fifth ligand coordinated to tin may be either a hydroxyl group or a surface O2- ion: formation of (> Al0)(> Al0H)Sn(n-C4H9)3 and of (>AlO)-(>AlO2~)Sn(n-C4H9)3. The complexity of these resonances and the dependence thereof on the type of alumina used and the degree of dehydroxylation are attributed to the influence of the geometry of neighboring aluminum atoms on the tin chemical shift. These results apply the extreme sensitivity of tin chemical shifts to molecular enviroment, producing a method whereby surface organometallic complexes of tin can be used as molecular probes for determining surface structures of oxides. The 119Sn NMR is shown to be much more sensitive than other previously used spectroscopic techniques, such as IR, Raman, and 29Al NMR.
UR - http://www.scopus.com/inward/record.url?scp=0000879355&partnerID=8YFLogxK
U2 - 10.1021/ja00098a025
DO - 10.1021/ja00098a025
M3 - Article
AN - SCOPUS:0000879355
SN - 0002-7863
VL - 116
SP - 8638
EP - 8646
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 19
ER -