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The Influence of β‐diiminato Ligands on As 4 Activation by Cobalt Complexes
Author(s) -
Spitzer Fabian,
Balázs Gábor,
Graßl Christian,
Keilwerth Martin,
Meyer Karsten,
Scheer Manfred
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201802888
Subject(s) - steric effects , reactivity (psychology) , chemistry , cobalt , crystallography , octahedron , yield (engineering) , single crystal , stereochemistry , nuclear magnetic resonance spectroscopy , atom (system on chip) , crystal structure , materials science , inorganic chemistry , medicine , alternative medicine , pathology , computer science , metallurgy , embedded system
Abstract In a systematic study of the activation of As 4 , three [LCo(tol)] (L=β‐diiminato) complexes have revealed different steric and electronic influences. 2,6‐Diisopropylphenyl (Dipp) and 2,6‐dimethylphenyl (dmp) flanking groups were used, one of the ligands with H backbone substituents (β‐dialdiminate L 0 ) and two with Me substituents (β‐diketiminates L 3 and L 1 ). In the reaction with As 4 , different dinuclear products [(LCo) 2 As 4 ] (LM=L 0 ( 1 ), L 1 ( 2 ), L 3 ( 3 )) were isolated, with all showing differently shaped [Co 2 As 4 ] cores in the solid state: octahedral in 1 , prismatic in 2 , and asterane‐like in 3 . Thermal treatment of 3 leads to the abstraction of one arsenic atom to yield [(L 3 Co) 2 As 3 ] ( 4 ). All products were comprehensively characterized by single‐crystal X‐ray diffraction, FD‐MS, and 1 H NMR spectroscopy. A rational explanation for the different reactivity is also proposed and DFT calculations shed light on the nature of the highly flexible [Co 2 As 4 ] cores.