Limits...
mer -Tri ­ chlorido ­ tris ­ (tetra ­ hydro ­ thio ­ phene- κ S )iridium(III): preparation and comparison with other mer -tri ­ chlorido ­ tris ­ (tetra ­ hydro ­ thio ­ phene- κ S )metal complexes

View Article: PubMed Central - HTML - PubMed

ABSTRACT

The title complex, [IrCl3(C4H8S)3], was prepared according to a literature method. A suitable crystal was obtained by diffusion of pentane into a di­chloro­methane solution and analyzed by single-crystal X-ray diffraction at 100 K. The title complex is isotypic with mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)rhodium(III). However, the orientation of the tetra­hydro­thio­phene rings is different from an earlier report of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) deposited in the Cambridge Structural Database. The IrS3Cl3 core shows a nearly octa­hedral structure with various bond angles within 1–2° of the perfect 90 or 180° expected for an octa­hedron. The structure of the title compound is compared with the previous iridium complex as well as the rhodium and other octa­hedral metal tris-tetra­hydro­thio­phene compounds previously structurally characterized. DFT calculations were performed, which indicate the mer isomer is significantly lower in energy than the fac isomer by 50.1 kJ mol−1, thereby accounting for all compounds in the CSD being of the mer geometry. Powder X-ray diffraction of the bulk material showed that the preparation method yielded only the isomorph reported in this communication.

No MeSH data available.


Calculated overlay of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) (CCDC 1495966) in yellow with the isotypical rhodium complex (CCDC GEZHUO) in blue.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC5120713&req=5

fig3: Calculated overlay of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) (CCDC 1495966) in yellow with the isotypical rhodium complex (CCDC GEZHUO) in blue.

Mentions: A survey of the CCDC database (Groom et al., 2016 ▸) uncovered a number of metal mer-tris­(THT-κS)metal complexes (THT= tetra­hydro­thio­phene), including one iridium structure deposited as a private communication (CCDC 1438699; Rheingold & Donovan-Merkert, 2015 ▸). The deposited structure (CCDC 1438699) packs with very different unit-cell parameters but the overall mol­ecular structure is substanti­ally the same. The results of the different packing, however, are slightly different conformations of two of the three THT ligands, as shown in Fig. 2 ▸, a structure overlay calculated in Mercury (Macrae et al., 2008 ▸). On the other hand, the rhodium(III) complex is isotypic with the title complex with similar unit-cell parameters (CCDC refcode GEZHUO; Clark et al., 1988 ▸). Fig. 3 ▸ shows an overlay calculated with Mercury (Macrae et al., 2008 ▸) of the title complex with the rhodium compound, showing the nearly perfect atomic overlay. Ruthenium(III) (VIJYAO; Yapp et al., 1990 ▸) and molybdenum(III) (REDXIH; Boorman et al., 1996 ▸) complexes were also found in the database, with all showing the same meridional arrangement of ligands with the exception that the ruthenium complex displays disorder from overlapping conformations of one of the THT ligands.


mer -Tri ­ chlorido ­ tris ­ (tetra ­ hydro ­ thio ­ phene- κ S )iridium(III): preparation and comparison with other mer -tri ­ chlorido ­ tris ­ (tetra ­ hydro ­ thio ­ phene- κ S )metal complexes
Calculated overlay of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) (CCDC 1495966) in yellow with the isotypical rhodium complex (CCDC GEZHUO) in blue.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5120713&req=5

fig3: Calculated overlay of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) (CCDC 1495966) in yellow with the isotypical rhodium complex (CCDC GEZHUO) in blue.
Mentions: A survey of the CCDC database (Groom et al., 2016 ▸) uncovered a number of metal mer-tris­(THT-κS)metal complexes (THT= tetra­hydro­thio­phene), including one iridium structure deposited as a private communication (CCDC 1438699; Rheingold & Donovan-Merkert, 2015 ▸). The deposited structure (CCDC 1438699) packs with very different unit-cell parameters but the overall mol­ecular structure is substanti­ally the same. The results of the different packing, however, are slightly different conformations of two of the three THT ligands, as shown in Fig. 2 ▸, a structure overlay calculated in Mercury (Macrae et al., 2008 ▸). On the other hand, the rhodium(III) complex is isotypic with the title complex with similar unit-cell parameters (CCDC refcode GEZHUO; Clark et al., 1988 ▸). Fig. 3 ▸ shows an overlay calculated with Mercury (Macrae et al., 2008 ▸) of the title complex with the rhodium compound, showing the nearly perfect atomic overlay. Ruthenium(III) (VIJYAO; Yapp et al., 1990 ▸) and molybdenum(III) (REDXIH; Boorman et al., 1996 ▸) complexes were also found in the database, with all showing the same meridional arrangement of ligands with the exception that the ruthenium complex displays disorder from overlapping conformations of one of the THT ligands.

View Article: PubMed Central - HTML - PubMed

ABSTRACT

The title complex, [IrCl3(C4H8S)3], was prepared according to a literature method. A suitable crystal was obtained by diffusion of pentane into a di­chloro­methane solution and analyzed by single-crystal X-ray diffraction at 100 K. The title complex is isotypic with mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)rhodium(III). However, the orientation of the tetra­hydro­thio­phene rings is different from an earlier report of mer-tri­chlorido­tris­(tetra­hydro­thio­phene-κS)iridium(III) deposited in the Cambridge Structural Database. The IrS3Cl3 core shows a nearly octa­hedral structure with various bond angles within 1–2° of the perfect 90 or 180° expected for an octa­hedron. The structure of the title compound is compared with the previous iridium complex as well as the rhodium and other octa­hedral metal tris-tetra­hydro­thio­phene compounds previously structurally characterized. DFT calculations were performed, which indicate the mer isomer is significantly lower in energy than the fac isomer by 50.1 kJ mol−1, thereby accounting for all compounds in the CSD being of the mer geometry. Powder X-ray diffraction of the bulk material showed that the preparation method yielded only the isomorph reported in this communication.

No MeSH data available.