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Methyllead(IV) Derivatives Stabilized by DAPTSC 2– : Synthesis and Structures of New Diorganolead(IV) Complexes
Author(s) -
Casas José S.,
Castellano Eduardo E.,
Ellena Javier,
GarcíaTasende María S.,
Namor Facundo,
Sánchez Agustín,
Sordo José,
Vidarte María J.
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700096
Subject(s) - chemistry , octahedron , pentagonal bipyramidal molecular geometry , coordination sphere , pyridine , semicarbazone , molecule , crystallography , crystal structure , stereochemistry , medicinal chemistry , lone pair , methanol , bipyramid , trigonal bipyramidal molecular geometry , metal , organic chemistry
The reaction of the bis(thiosemicarbazone) of dimethyl pyridine‐2,6‐diyl diketone, H 2 DAPTSC, with PbMe 2 (OAc) 2 , PbMePh(OAc) 2 or PbPh 2 (OAc) 2 in MeOH afforded the complexes [PbMe 2 (DAPTSC)], [PbMePh(DAPTSC)] or [PbPh 2 (DAPTSC)] (in the first two cases together with [Pb(DAPTSC)]). X‐ray crystallography of the Pb(IV) complexes showed that the metal has a pentagonal bipyramidal coordination sphere. The N 3 ,S 2 ‐bound DAPTSC 2– anion occupied the equatorial plane and the organic groups were in the apical positions. These compounds retain the same coordination mode in DMSO solution. DAPTSC 2– is also N 3 ,S 2 ‐bound in [Pb(DAPTSC)], a complex with a stereochemically active Pb II lone pair. The reaction of PbPh 2 Cl 2 with H 2 DAPTSC, also in methanol at room temperature, afforded [PbPh 2 (H 2 DAPTSC)] 2 [PbPh 2 Cl 4 ]Cl 2 · 6CH 3 OH. X‐ray crystallography of this centrosymmetric complex showed it to consist of two [PbPh 2 (H 2 DAPTSC)] 2+ cations of similar structure to the neutral [PbR 2 (DAPTSC)] complexes, together with a trans ‐octahedral [PbPh 2 Cl 4 ] 2– anion and two Cl – anions. This compound decomposes in DMSO solution, probably evolving to H 2 DAPTSC and PbPh 2 Cl 2 (DMSO) n . In order to evaluate the changes undergone by H 2 DAPTSC under metallation, the X‐ray structure of the free molecule was also determined.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)