Affiliation:
1. Institute of Inorganic Chemistry University of Regensburg 93040 Regensburg Germany
2. Institute of Inorganic Chemistry Karlsruhe Institute of Technology (KIT) Engesserstraße 15 76131 Karlsruhe Germany
3. School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram Thiruvananthapuram 695551 Kerala India
4. Institute of Chemistry Saint Petersburg State University Universitetskaya emb. 7/9 199034 St. Petersburg Russia
Abstract
AbstractThe reaction behavior of [Cp*Fe(η5‐As5)] (I) (Cp*=C5Me5) towards carbenes and their heavier analogs was investigated. The reaction of I with NHCs (NHCs=N‐heterocyclic carbenes) results in the first substitution products of polyarsenic ligand complexes by NHCs [Cp*Fe(η4‐As5NHC)] (1 a: NHC=IMe=1,3,4,5‐tetramethylimidazolin‐2‐ylidene, 1 b: NHC=IMes=1,3‐bis(2,4,6‐trimethylphenyl)‐imidazolin‐2‐ylidene). In contrast, the reaction of I with EtCAAC (EtCAAC=2,6‐diisopropylphenyl)‐4,4‐diethyl‐2,2‐dimethyl‐pyrrolidin‐5‐ylidene) leads to a fragmentation and the formation of an unprecedented As6‐sawhorse‐type compound [As2(AsEtCAAC)4] (2). The reaction of (LE)2 (L=PhC(NtBu)2; E=Si, Ge) with I resulted in a rearrangement and an insertion of LE fragments, forming unique silicon‐ (4: [Cp*Fe(η4‐As4SiL)], 5 a: [Cp*Fe(η4‐As6SiL)) and germanium‐containing (5 b: [Cp*Fe(η4‐As6GeL)) cyclic polyarsenic ligand complexes.
Funder
Deutsche Forschungsgemeinschaft
Subject
General Chemistry,Catalysis