Premium
Square Planar Coordination of Silver in a η 4 ‐Cyclobutadiene‐(η 5 ‐C 5 H 5 )ReBr 2 Complex Framework
Author(s) -
Kleinschmidt Steffen,
Hinz Alexander,
Villinger Alexander,
Seidel Wolfram W.
Publication year - 2018
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201800266
Subject(s) - cyclobutadiene , chemistry , halide , crystallography , moiety , cationic polymerization , bromide , ligand (biochemistry) , metal , rhenium , stereochemistry , substituent , inorganic chemistry , molecule , polymer chemistry , organic chemistry , biochemistry , receptor
Halide addition and abstraction experiments with the cationic rhenacyclopentatriene [(η 5 ‐C 5 H 5 ){ReC 4 (SBn) 4 }Br]BF 4 and the side‐on cyclobutadiene complexes [(η 5 ‐C 5 H 5 )(η 4 ‐C 4 Ph 4 )Re X 2 ] ( X = Br, I), respectively, are described. Reversible interconversion of both coordination modes of the metal bonded C 4 R 4 moiety depending on the presence or absence of the second bromide ligand is demonstrated for the sulfide derivative. However, formation of the [(η 5 ‐C 5 H 5 )(ReC 4 Ph 4 ) X ] + congener by halide abstraction at [(η 5 ‐C 5 H 5 )(η 4 ‐C 4 Ph 4 )Re X 2 ] turned out to be impossible. Instead, formation of silver halide complexes with the halide bridging rhenium and silver under retention of the metalorganic scaffold are observed. Governed by the phenyl substituent framework a square‐planar coordination environment about the Ag cation is adopted for X = Br. Changing X = Br by X = I led to the formation of a heptanuclear complex with di‐ and three‐coordinate silver ions.