The synthesis, characterization and substitution reactions of the mixed ligand technetium(I) nitrosyl complex trans-trans-[(NO)(NCCH3)Cl-2(PPh(3))(2)Tc]
The synthesis, characterization and substitution reactions of the mixed ligand technetium(I) nitrosyl complex trans-trans-[(NO)(NCCH3)Cl-2(PPh(3))(2)Tc]
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DOI：
10.1016/0020-1693(95)04755-7
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发表时间：
1996-03-01
影响因子：
2.8
通讯作者：
Jones, AG
中科院分区：
文献类型：
--
作者：
Blanchard, SS;Nicholson, T;Jones, AG
The technetium-nitrosyl complex n-Bu(4)N[Tc(NO)Cl-4] reacts with excess triphenylphosphine in refluxing acetonitrile to give the Tc(I) mixed ligand complex [Tc(NO)Cl-2(PPh(3))(2)NCCH3] in good yield. The IR spectrum of this complex displays an absorption at 1690 cm(-1) which is associated with upsilon(NO). The FAB(+) mass spectrum shows the fragment of 723 m/z which corresponds to [Tc(NO)Cl-2(PPh(3))(2)](+) which is generated from the loss of the acetonitrile ligand. The H-1 NMR spectrum of this species displays equivalent trans-triphenylphosphine ligands; however because of the lability of the acetonitrile ligand, two signals are observed from the coordinated and dissociated acetonitrile protons. The analogous reaction in methanol gives the methanol adduct [Tc(NO)Cl-2(PPh(3))(2)HOCH3]. When pyridine is employed as solvent, the tris-pyridine complex [Tc(NO)Cl-2(py)3] is isolated as the major product, with no phosphine coordination. The LR spectrum of this complex shows an absorption at 1688 cm(-1) which is associated with upsilon(NO). The FAB(+) mass spectrum shows the fragment of 436 m/z which corresponds to the parent ion [Tc(NO)Cl-2(py)(3)](+). This diamagnetic Tc(I) complex displays a well resolved, narrow-lined H-1 NMR spectrum. Crystal data for [Tc(NO)Cl-2(py)(3)]. 2CH(3)CN: monoclinic space group C2/c, (No. 15), a=19.182(1), b=10.8725(8), c=11.9371(8) Angstrom, beta=116.580(7)degrees, V=2226.5(6) Angstrom(3), with D-calc=1.543 g cm(-3) to give Z=4. Structure solution based on 2689 reflections converged at R=0.025, R(w)=0.030, GOF=1.41. The reaction chemistry of the acetonitrile adduct [Tc(NO)Cl-2(PPh(3))(2)NCCH3] with pyridine, 3,5-lutidine, bipyridine, phenanthroline and terpyridine is also presented.
