Balasekaran S M, Hagenbach A, Drees M, Abram U
Freie Universität Berlin, Institute of Chemistry and Biochemistry, Fabeckstr. 34/36, 14195 Berlin, Germany.
Dalton Trans. 2017 Oct 10;46(39):13544-13552. doi: 10.1039/c7dt03084c.
Fluoridotetrakis(trifluoroacetato)nitrosyltechnetate(ii) was prepared by the dissolution of Cs[Tc(NO)F] in trifluoroacetic acid and addition of (NBu)F·3HO. The compound crystallizes as a mixed Cs/NBu salt in the form of green crystals. Unlike the [Tc(NO)F] salts, the product is soluble in organic solvents and can be used as a precursor for ongoing ligand exchange procedures with organic ligands. The corresponding reactions with triphenylphosphine (PPh), 1,2-bis(diphenylphosphino)ethane (DPPE) or pyridyldiphenylphosphine (pyPPh) give technetium(i) complexes of the compositions Cs[Tc(NO)(PPh)(CFCOO)F], Tc(NO)(DPPE)(OOCCF) and [Tc(NO)(κN,P-pyPPh)(κP-pyPPh)(CFCOO)]. The products were studied spectroscopically and by X-ray diffraction. The Tc NMR resonances of the novel Tc(i) nitrosyls appear between -627 and +952 ppm, which is at a remarkably high field and in the range where normally the signals of Tc(iii) compounds are observed.
二价氟代四（三氟乙酸根）亚硝酰锝酸盐通过将Cs[Tc(NO)F]溶解于三氟乙酸中并加入(NBu)F·3HO来制备。该化合物以Cs/NBu混合盐的形式结晶为绿色晶体。与[Tc(NO)F]盐不同，该产物可溶于有机溶剂，并且可用作与有机配体进行配体交换过程的前体。与三苯基膦（PPh）、1,2-双（二苯基膦基）乙烷（DPPE）或吡啶基二苯基膦（pyPPh）的相应反应生成组成分别为Cs[Tc(NO)(PPh)(CFCOO)F]、Tc(NO)(DPPE)(OOCCF)和[Tc(NO)(κN,P-pyPPh)(κP-pyPPh)(CFCOO)]的锝（Ⅰ）配合物。通过光谱学和X射线衍射对产物进行了研究。新型锝（Ⅰ）亚硝酰化合物的Tc NMR共振出现在-627至+952 ppm之间，这处于非常高的场强，且在通常观察到Tc(Ⅲ)化合物信号的范围内。
