TY - JOUR
T1 - Multiple Bonds between Main-Group Elements and Transition Metals. 137.1 Polymeric Methyltrioxorhenium
T2 - An Organometallic Nanoscale Double-Layer Structure of Corner-Sharing ReO5(CH3) Octahedra with Intercalated Water Molecules
AU - Mertin, Wilhelm
AU - Gruehn, Reginald
AU - Mink, Janos
AU - Boysen, Hans
AU - Herrmann, Wolfgang A.
AU - Scherer, Wolfgang
AU - Bliimel, Janet
AU - Kleine, Matthias
AU - Mattner, Mike
AU - Fischer, Richard W.
AU - Wilson, Chick C.
AU - Ibberson, Richard M.
AU - Bachmann, Luis
PY - 1995/3
Y1 - 1995/3
N2 - A two-dimensional structural model of polymeric methyltrioxorhenium (MTO) has been established by means of diffraction techniques and a variety of analytical methods. The unusual compound, constituting the first example of a polymeric organometallic oxide, has a layer structure of methyl-deficient, comer-sharing ReO5(CH3) octahedra. It adopts the three-dimensional extended ReO3 motif in two dimensions as a {ReO2}∞ network. Adjacent layers of corner-sharing ReO5(CH3) octahedra (A) are capable of forming staggered double layers (AA'). In the crystalline areas of “poly-MTO”, such double layers are separated by intercalated water molecules (monolayer) (B) with an. AA'BAA'. layer sequence. For the partially amorphous areas of “poly-MTO”, we propose a turbostratic and 00l-defect stacking model for the “poly-MTO” and water layers. Interactions between the adjacent layers in this polymeric MTO are very weak, resulting in graphite-like macroscopic properties such as flaky appearance, softness, and lubricity. High electric conductivity results from understoichiometry with respect to the CH3/Re ratio (9.2/10) and partial reduction by extra hydrogen equivalents. For the purpose of comparison, the solid-state structure of “monomeric” MTO as established by a combination of X-ray and powder neutron diffraction techniques is also reported.
AB - A two-dimensional structural model of polymeric methyltrioxorhenium (MTO) has been established by means of diffraction techniques and a variety of analytical methods. The unusual compound, constituting the first example of a polymeric organometallic oxide, has a layer structure of methyl-deficient, comer-sharing ReO5(CH3) octahedra. It adopts the three-dimensional extended ReO3 motif in two dimensions as a {ReO2}∞ network. Adjacent layers of corner-sharing ReO5(CH3) octahedra (A) are capable of forming staggered double layers (AA'). In the crystalline areas of “poly-MTO”, such double layers are separated by intercalated water molecules (monolayer) (B) with an. AA'BAA'. layer sequence. For the partially amorphous areas of “poly-MTO”, we propose a turbostratic and 00l-defect stacking model for the “poly-MTO” and water layers. Interactions between the adjacent layers in this polymeric MTO are very weak, resulting in graphite-like macroscopic properties such as flaky appearance, softness, and lubricity. High electric conductivity results from understoichiometry with respect to the CH3/Re ratio (9.2/10) and partial reduction by extra hydrogen equivalents. For the purpose of comparison, the solid-state structure of “monomeric” MTO as established by a combination of X-ray and powder neutron diffraction techniques is also reported.
UR - http://www.scopus.com/inward/record.url?scp=0000433711&partnerID=8YFLogxK
U2 - 10.1021/ja00116a027
DO - 10.1021/ja00116a027
M3 - Article
AN - SCOPUS:0000433711
SN - 0002-7863
VL - 117
SP - 3231
EP - 3243
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 11
ER -