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Nacnac‐Cobalt‐Mediated P 4 Transformations
Author(s) -
Spitzer Fabian,
Graßl Christian,
Balázs Gábor,
Mädl Eric,
Keilwerth Martin,
Zolnhofer Eva M.,
Meyer Karsten,
Scheer Manfred
Publication year - 2017
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.201605451
Subject(s) - isostructural , cobalt , chemistry , cyclic voltammetry , electrochemistry , medicinal chemistry , derivative (finance) , atom (system on chip) , crystallography , stereochemistry , inorganic chemistry , crystal structure , electrode , computer science , financial economics , economics , embedded system
A comparison of P 4 activations mediated by low‐valent β‐diketiminato (L) cobalt complexes is presented. The formal Co 0 source [K 2 (L 3 Co) 2 (μ 2 :η 1 ,η 1 ‐N 2 )] ( 1 ) reacts with P 4 to form a mixture of the monoanionic complexes [K(thf) 6 ][(L 3 Co) 2 (μ 2 :η 4 ,η 4 ‐P 4 )] ( 2 ) and [K(thf) 6 ][(L 3 Co) 2 (μ 2 :η 3 ,η 3 ‐P 3 )] ( 3 ). The analogue Co I precursor [L 3 Co(tol)] ( 4 a ), however, selectively yields the corresponding neutral derivative [(L 3 Co) 2 (μ 2 :η 4 ,η 4 ‐P 4 )] ( 5 a ). Compound 5 a undergoes thermal P atom loss to form the unprecedented complex [(L 3 Co) 2 (μ 2 :η 3 ,η 3 ‐P 3 )] ( 6 ). The products 2 and 3 can be obtained selectively by an one‐electron reduction of their neutral precursors 5 a and 6 , respectively. The electrochemical behaviour of 2 , 3 , 5 a , and 6 is monitored by cyclic voltammetry and their magnetism is examined by SQUID measurements and the Evans method. The initial Co I ‐mediated P 4 activation is not influenced by applying the structurally different ligands L 1 and L 2 , which is proven by the formation of the isostructural products [(LCo) 2 (μ 2 :η 4 ,η 4 ‐P 4 )] [L=L 3 ( 5 a ), L 1 ( 5 b ), L 2 ( 5 c )].