Paramagnetic adduct formation of pyridine with nickel(II)-bis(di-n-butyl-diselenocarbamate) is observed by means of EPR at 27°K. The low value of the zero field splitting and the g-factor are explained by strong spin-orbit interactions and by high covalency typical of the Se4-coordination sphere. © 1973

Bottcher R.

Kirmse R.

Wartewig S.

Chemical Physics Letters

Kazan Federal University Digital Repository

Volume 22, number 2 CHEMICAL PHYSICS LETTERS 1 October 1973 1. Introduction Planar Ni(II)-chelates are frequently found to ex- ON THE EXISTENCE OF A PARAMAGNETIC ADDUCT OF Ni( II)-BIS-( DI-n-BUTY L-DISELENOCARBAMATE). AN EPR STUDY R. KlRMSE” Physics Department, Kazan State University, 420008 Kazan, USSR and S. WARTEWIG and R. BOTTCHER Section of Physics, Karl-Marx-University, 701 Leipzig, GDR Received 18 April 1973 Revised manuscript received 18 July 1973 Paramagnetic adduct formation of pyridine with nickel(H)-bis(di-n-butyl-diselenocarbamate) is observed by means of EPR at 27°K. The low value of the zero field splitting and theg-factor are explained by strong spin-orbit interac- tions and by high covalency typical of the Sed-coordination sphere. pand their coordination number by interaction with a Lewis base forming paramagnetic high-spin adduct complexes: NiL, + 2L’ + trans-NiLqLi , (1) In contrast to the complexes of the coordination type NiO, which are known to create readily quasi-octa- hedral adducts, NiS4-complexes vary substantially in their ability to interact with Lewis bases. To our knowledge there is until now no direct evidence for the existenc;e of a paramagnetic adduct complex of Ni(II)-N,N-dialkyl-dithio- and diselenocarbamates [l-3] . Using EPR we have found that [Ni(dbsc)2] (dbsc = di-n-butyl-diselenocarbamate) forms a quasi- octahedral high-spin complex (I) in pyridine solution at 27°K. * Permanent address: Section of Chemistry, Karl-Marx- University, 701 Leipzig, GDR. 2. Experimental and results [Ni(dbscJ2] was prepared as described earlier [3]. 0.01.-0.02 M solutions of [Ni(dbsc)2] in chloroform containing about 30 vol-% pyridine were used. At- tempts to isolate [Ni(dbsc)2(pyr)1] brought no suc- cess. The EPR studies were carried out at X-band. In the liquid solution of (I) no EPR spectrum could be detected. The adduct formation is found to be re- markable at temperatures lower than 100°K. In the temperature range 120-77°K we could observe an EPR signal with low intensity. The intensity of the spectrum increases as the temperatures decreases. 427 

On the existence of a paramagnetic adduct of Ni(II)-bis-(di-n-butyl-diselenocarbamate). An EPR study

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On the existence of a paramagnetic adduct of Ni(II)-bis-(di-n-butyl-diselenocarbamate). An EPR study

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