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Heterobimetallic Systems Containing Organometallic and Classical Coordination Sites: Effects of Subtle Changes in the Werner‐Type Site
Author(s) -
Sheng Tianlu,
Dechert Sebastian,
Stückl A. Claudia,
Meyer Franc
Publication year - 2005
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/ejic.200400718
Subject(s) - chemistry , zinc , bimetallic strip , manganese , group 2 organometallic chemistry , electron paramagnetic resonance , redox , crystallography , organometallic chemistry , ligand (biochemistry) , amine gas treating , tris , stereochemistry , inorganic chemistry , metal , crystal structure , molecule , organic chemistry , receptor , nuclear magnetic resonance , biochemistry , physics
Several highly unsymmetrical heterodinuclear Mn/Zn complexes are reported, in which an organometallic CpMn‐(CO) 2 fragment and a classical Werner‐type zinc coordination unit are arranged in close proximity by means of a bridging pyrazolate. Ligand scaffolds differing in the chelate size of the tripodal tetradentate {N 4 } binding site, and different coligands for zinc are employed. Both the zinc‐devoid precursor compounds and the bimetallic complexes with zinc( II ) nested in the tris(pyridylalkyl)amine type {N 4 } compartment have been characterized by X‐ray crystallography. Structural and spectroscopic features as well as the redox potentials of the Mn I /Mn II couple indicate slight effects of the redox‐inactive Werner‐type subunit on the properties of the organometallic site. Oxidation is highly localized at the organometallic manganese site, as is evidenced by IR and EPR spectroscopy and supported by DFT calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)