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Nickel(II) N ‐Benzyl‐ N ‐methyldithiocarbamato Complexes as Precursors for the Preparation of Graphite Oxidation Accelerators
Author(s) -
Trávníček Zdeněk,
Pastorek Richard,
Štarha Pavel,
Popa Igor,
Slovák Václav
Publication year - 2010
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.201000091
Subject(s) - nickel , graphite , chemistry , molar conductivity , crystal structure , thermal analysis , catalysis , inorganic chemistry , crystallography , nuclear chemistry , elemental analysis , organic chemistry , thermal , physics , meteorology
The nickel(II) N ‐benzyl‐ N ‐methyldithiocarbamato (BzMedtc) complexes [Ni(BzMedtc)(PPh 3 )Cl] ( 1 ), [Ni(BzMedtc)(PPh 3 )Br] ( 2 ), [Ni(BzMedtc)(PPh 3 )I] ( 3 ), and [Ni(BzMedtc)(PPh 3 )(NCS)] ( 4 ) were synthesized using the reaction of [Ni(BzMedtc) 2 ] and [Ni X 2 (PPh 3 ) 2 ] ( X = Cl, Br, I and NCS). Subsequently, complex 1 was used for the preparation of [Ni(BzMedtc)(PPh 3 ) 2 ]ClO 4 ( 5 ), [Ni(BzMedtc)(PPh 3 ) 2 ]BPh 4 ( 6 ), and [Ni(BzMedtc)(PPh 3 ) 2 ]PF 6 ( 7 ). The obtained complexes 1 – 7 were characterized by elemental analysis, thermal analysis and spectroscopic methods (IR, UV/Vis, 31 P{ 1 H} NMR). The results of the magnetochemical and molar conductivity measurements proved the complexes as diamagnetic non‐electrolytes ( 1 – 4 ) or 1:1 electrolytes ( 5 – 7 ). The molecular structures of 4 and 5· H 2 O were determined by a single‐crystal X‐ray analysis. In all cases, the Ni II atom is tetracoordinated in a distorted square‐planar arrangement with the S 2 P X , and S 2 P 2 donor set, respectively. The catalytic influence of selected complexes 1 , 3 , 5 , and 6 on graphite oxidation was studied. The results clearly indicated that the presence of the products of thermal degradation processes of the mentioned complexes has impact on the course of graphite oxidation. A decrease in the oxidation start temperatures by about 60–100 °C was observed in the cases of all the tested complexes in comparison with pure graphite.