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Updated: Jun 14, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates
Till Erik Sawallisch1, Abdullah Abdulkader1, Domenik Nowak1
1Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany.
Abstract:
The very limited number of structurally known thionitrosyl complexes of technetium was increased by the synthesis of [TcII(NS)Cl3(PPh3)2] (3) and [TcII(NS)Cl3(PPh3)(OPPh3)] (4) and their reaction products with hydrotris(pyrazolyl)borates, {HB(pzR)3}-. Similar reactions were conducted with [TcI(NO)Cl2(PPh3)2(CH3CN)] and related rhenium thionitrosyls. Remarkably, most such reactions result in a rapid cleavage of the boron-nitrogen bonds of the ligands and the formation of pyrazole complexes of the two group 7 metals. Only one compound with an intact {HB(pzR)3}- ligand could be isolated: the technetium(I) complex [TcI(NO)Cl(PPh3){HB(pz)3}] (2). Other products show the coordination of one or four neutral pyrazole ligand(s) in the coordination spheres of technetium generated by thermal decomposition of the pyrazolylborates [TcI(NO)Cl2(PPh3)2(pzH)] (1) and [TcI(NS)Cl(pzHMe2)4]+ (5). Reactions with the corresponding thionitrosylrhenium complex [ReII(NS)Cl3(PPh3)2] require higher temperatures and only compounds with one pyrazole ligand, [ReI(NS)Cl2(PPh3)(pzHR)] (6a-6c), were isolated. The products were studied spectroscopically and by X-ray diffraction.
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