Sy. Yang et al., Geometric features and electronic structures of six-coordinated dialkyl and dithiolate complexes of osmium(IV) porphyrins, ORGANOMETAL, 20(14), 2001, pp. 3198-3201
The majority of sir-coordinate d(4) osmium/ruthenium(IV) porphyrin complexe
s [M(por)X-2] have been found to be paramagnetic and have linear X-M-X stru
ctural units. However, an exception is found for [Os-(por)R-2] and [Os(por)
(SR)(2)] (R = alkyl), which are diamagnetic. While the S-Os-S unit in [Os(p
or)(SR)(2)] is linear, the R-Os-R unit in [Os(por)R-2] is found to be signi
ficantly bent. In this note, the geometric features and electronic structur
es of the dialkyl and dithiolate complexes of osmium(IV) porphyrins have be
en investigated by density functional calculations.