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Gold(I) Thiolates as Metalloligands for the Synthesis of the First Zirconocene−Gold Complexes
Author(s) -
Wenzel Barbara,
Lönnecke Peter,
HeyHawkins Evamarie
Publication year - 2002
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 - 10.1002/1099-0682(200207)2002:7<1761::aid-ejic1761>3.0.co;2-n
Subject(s) - chemistry , denticity , catalysis , crystal structure , metal , nuclear magnetic resonance spectroscopy , stereochemistry , crystallography , spectroscopy , medicinal chemistry , organic chemistry , physics , quantum mechanics
The reactions of the mercaptocarboxylic acids HOOC(CH 2 ) n SH ( n = 1, 2) with H[AuCl 4 ] followed by treatment with PMe 2 Ph led to the (phosphane)gold thiolates [Au{S(CH 2 ) n COOH}(PMe 2 Ph)] [ n = 1, ( 1 ) 2 ( 2 )], which can act as metalloligands towards complex fragments of a second metal. Compounds 1 and 2 react with [Cp° 2 ZrMe 2 ] (Cp° = C 5 EtMe 4 ) to give the trinuclear Zr/Au complexes [Cp° 2 Zr{κ 1 O ‐OOC(CH 2 ) n SAu(PMe 2 Ph)}{κ 2 O,O′ ‐OOC(CH 2 ) n SAu(PMe 2 Ph)}] [ n = 1 ( 3 ), n = 2 ( 4 )]. Complexes 1 − 4 were characterized by 1 H, 13 C, 31 P NMR and IR spectroscopy. The crystal structure of 4 shows mono‐ and bidentate coordination of two metalloligands to one zirconocene fragment. In solution at room temperature 3 and 4 are dynamic, and the carboxylato groups alternate between the mono‐ and bidentate bonding modes. Complex 4 shows catalytic activity in the oxidation of PPh 3 with O 2 . (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)