Metal-rich, neutral and cationic organotin clusters

Angewandte Chemie - International Edition

Volumn 44, Issue 17, 2005, Pages 2546-2549

  Richards, Anne F ^a   Eichler, Barrett E ^a   Brynda, Marcin ^a   Olmstead, Marilyn M ^a   Power, Philip P ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Cluster compounds; Density functional calculations; Structure elucidation; Tin

Indexed keywords

BONDING; CHARACTERIZATION; ORGANOMETALLICS; POSITIVE IONS; PROBABILITY DENSITY FUNCTION; SALTS;

CATIONIC ORGANOTIN CLUSTERS; METAL-RICH ORGANOTIN CLUSTERS; SPECIES; ZINTL SALTS;

TIN;

EID: 18044396757     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500117     Document Type: Article

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29. - at a site of 222 symmetry and disordered PhMe at a site of 2/m symmetry. The anion is fully ordered, and PhMe was refined as a rigid group at the multiplicity of the site (0.25 occupancy) with isotropic thermal parameters. In the cation, there are two anomalies which lower the symmetry of the cluster. One of the Sn atoms (Sn5) is clearly at half occupancy and Sn4 occupies two sites in the ratio Sn4:Sn4′:0.75:0.25, which was established by refinement. The three atoms Sn4, Sn4A, and Sn4B are symmetry-related positions for the major atom of the site shared by Sn4 and Sn4′. The minor atom, Sn4′, is drawn such that it occupies the side of the cluster where Sn5 is absent to avoid unrealistically short bonds. In the average structure, Sn4′ would occupy all four positions related by mm symmetry, and Sn5 (which resides on a mirror plane) would be reflected to the opposite side as well. These various distortions in the cluster may be the cause of disorder in the R group beginning with the atom C1. The atoms that make up this group are disordered with respect to a mirror plane that passes through the ipso carbon C1 and the para carbon C4 of the C1 aryl ring. This gives the appearance of large thermal motions perpendicular to this plane. To better describe this group, the atoms C1 and C4 were shifted off the mirror and the remainder of the atoms in this group located from a difference Fourier map. Thus, the atoms C1-C24 were refined at 0.5 occupancy with isotropic thermal parameters and a SHELXL PART-1 statement.
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