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Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates.


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.

SUBMITTER: Sawallisch TE 

PROVIDER: S-EPMC11357682 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Nitrosyl and Thionitrosyl Complexes of Technetium and Rhenium and Their Reactions with Hydrotris(pyrazolyl)borates.

Sawallisch Till Erik TE   Abdulkader Abdullah A   Nowak Domenik D   Hagenbach Adelheid A   Abram Ulrich U  

Molecules (Basel, Switzerland) 20240815 16


The very limited number of structurally known thionitrosyl complexes of technetium was increased by the synthesis of [Tc<sup>II</sup>(NS)Cl<sub>3</sub>(PPh<sub>3</sub>)<sub>2</sub>] (<b>3</b>) and [Tc<sup>II</sup>(NS)Cl<sub>3</sub>(PPh<sub>3</sub>)(OPPh<sub>3</sub>)] (<b>4</b>) and their reaction products with hydrotris(pyrazolyl)borates, {HB(pz<sup>R</sup>)<sub>3</sub>}<sup>-</sup>. Similar reactions were conducted with [Tc<sup>I</sup>(NO)Cl<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>(CH<sub>3</su  ...[more]

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