Metallorganische Lewis-Säuren. L. Addition von Pentacarbonylrhenium- und Triphenylphosphangold-Kationen an anionische Dithiolato-Metall-Komplexe als S-Nukleophile |
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| Authors: | Elke Fritsch,Kurt Polborn,Christian Robl,Karlheinz Sü nkel,Wolfgang Beck |
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| Abstract: | Organometallic Lewis Acids. L. Addition of Pentacarbonylrhenium and Triphenylphosphinegold Cations to Anionic Dithiolato Metal Complexes as S-Nucleophiles The organometallic Lewis Acids Ph3PAuNO3 ( 1 ) and (CO)5ReFBF3 ( 2 ) react with the dithiolato metal complexes (Bu4N)2[M(mnt)2] (mnt = m aleo n itrildi t hiolato, M = Ni, Cu, Pt, Zn) and (Bu4N)2[Zn(dmit)2] (dmit = d i m ercapto i sotri t hiono) to give the complexes (Ph3PAu)2mnt ( 3 ), (Bu4N)[Ph3PAu(mnt)] ( 4 ), (Ph3PAu)2Pt(mnt)2 ( 5 ), (Ph3PAu)2dmit ( 10 ) and [(CO)5Re]2Ni(mnt)2 ( 6 ), (Bu4N){[(CO)5Re]M(mnt)2} (M = Ni, Pt, 7, 8 ), [(CO)5Re]2(mnt)2 ( 9 ) and [(CO)5Re]2Ni(dmit)2 ( 11 ), respectively. The compounds 3, 4 and 5 have been characterized by x-ray structural analysis. In 4 the chelate ligand is symmetrically coordinated to the AuI atom. Weak Au? Au (dAu? Au = 309 pm) interactions lead to the formation of chains in the crystal of 3 . The trans-anti configuration in 5 can also be assumed for the complexes 6 and 11 for sterical reasons. Compound 1 reacts with K2[M(dto)2] (dto = d i t hio o xalato, M = Pd, Pt) to give the expected bis(triphenylphosphinegold) adducts 12 and 13 . Complex 2 , however, affords with dithiooxalato metal dianions the compound [(CO)5Re]2(dto)2 ( 14 ) as final product. (Ph3PAu)2dto ( 15 ) is obtained by reaction of 1 with K2dto. [(CO)5Re]2FeNO(dto)2 ( 16 ) can be isolated as an unstable adduct from the reaction of 2 with [Fe(NO)(dto)2]2? Re(CO)5+ and Ph3PAu+ can be added to the bridging S atoms of [(ON)2Fe(μ-S)2Fe(NO)2]2? to give 17 and 18 |
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| Keywords: | Dithiolato metal complexes pentacarbonyl-rhenium triphosphinegold preparation crystal structure |
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