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Versatile Coordination of Ag I and Cu I Ions towards cyclo ‐As 5 Ligands
Author(s) -
Moussa Mehdi Elsayed,
Fleischmann Martin,
Balázs Gábor,
Virovets Alexander V.,
Peresypkina Eugenia,
Shelyganov Pavel A.,
Seidl Michael,
Reichl Stephan,
Scheer Manfred
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101096
Subject(s) - ion , chemistry , crystallography , coordination number , solid state , coordination complex , gas phase , stereochemistry , metal , organic chemistry
The reactions of the cyclo ‐As 5 complex [Cp*Fe(η 5 ‐As 5 )] ( B ) with the Ag I and Cu I salts of the weakly coordinating anion (WCA) [FAl{OC 6 F 10 (C 6 F 5 )} 3 ] − ([FAl] − ) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η 5 : η 2 ‐ B ) 2 ][FAl] (M=Ag ( 1 ), Cu ( 2 )) when a ratio of B /M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central Ag I cation between two π‐coordinating cyclo ‐As 5 ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo‐As 5 ligands in B . When the ratio of B /Ag(FAl) is changed to 3 : 1 or 1 : 1, the respective coordination compounds [Ag(η 2 ‐ B ) 3 ][FAl] ( 3 ) and [Ag 2 (η 2 : η 2 ‐ B ) 2 ][FAl] 2 ( 4 ) are accessible. The coordination modes of the cyclo ‐As 5 units in 1 , 3 and 4 are all different, reflecting the adaptive coordination behavior of B towards Ag I ions. The optimized geometries in the gas phase of 1 – 4 are determined by DFT calculations to support the bonding situation observed in their solid‐state structures.