Notes. A spectroscopic and crystallographic study of the [ReNCl4]? ion

Abstract

The crystal structure and the i.r. spectra reveal the nearly ideal C,, symmetry of the [ReNCIJ-ion. The force constant of the Re-N bond is in agreement with the observed ReZN length of 1.61 9(10) A. The Re-CI bond distance, 2.322(2) A, is the first to be reported for a ReV1 case. Unit-cell parameters are in close agreement with those of the other members of the isostructural series: a = 12.776(4), c = 7.778(3) A, Z = 2, and 0, = 1.90 g ~m -~ in the tetragonal space group P4/n. Least-squares refinement gave a final R value of 0.022 for 534 unique observed reflections.COMPLEXES of the [MNCl,]-ion are well known for the transition metals molybdenum, tungsten, ruthenium, and o s m i ~m . l -~ Some of their tetraphenylarsonium derivatives have been characterized by X-ray crystallographic determinations. The complexes contain metal-nitrogen triple bonds (symmetry &), as shown by the short metal-nitrogen bond lengths [MoSN, 1.66(1)

Final Report, Research Program to Investigate the Fundamental Chemistry of Technetium

“…In order to pursue these investigations, however, it was first necessary to devise improved methods for preparation of common starting materials. A number of technetium and rhenium complexes possessing terminal oxo or nitrido groups and halide ligands have been reported in the literature, but their widespread use has been hindered by difficult and low-yield syntheses (Cotton 1979, Davison 1982, Nelson 1954, Rulfs 1955, Liese 1981, Baldas 1991, Cotton 1966, Rose 1996, Baldas 1984 -, and MOX 3 (L) 2 (M = Tc, Re; X = Cl, Br, I; L = THF, MeCN) were devised. Vibrational and electronic spectroscopies proved best suited to characterize the metal oxohalide complexes; EPR spectroscopy was also utilized to examine the paramagnetic species in the series.…”

Synthese und Struktur der Komplexe [(n-Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N-PdCl(μ-Cl)]2 und [(n-Bu)4N]2[Pd3Cl8]

“…Zu 140 mg PdCl 2 (NCC 6 H 5 ) 2 (0,365 mmol), gelöst in 8 ml THF, werden 420 mg [(n-Bu) 4 [ (n-Bu) 4 N] 2 [Pd 3 Cl 8 …”

“…In 3 liegen zwei symmetrieunabhängige, planare Dreikernkomplexe [Pd 3 Cl 8 ] 2Ϫ mit der Symmetrie 1 vor, in denen die Pd-Atome über schwach asymmetrische Chlorobrücken verknüpft sind. 4 ReϵN-PdCl(µ-Cl)] 2 (2) erhalten.…”

“…Die Abstände in den Nitridobrücken betragen Re-N ϭ 163,8(9) pm und Pd-N ϭ 191,5(9) pm. plexes [Pd 3 Cl 8 ] 2Ϫ with the symmetry 1, in which the Pd atoms are connected by slightly asymmetric chloro bridges. [ (n-Bu) 4 …”

Nitrido-und Oxochlorokomplexe des Vanadiums(V); die Kristallstruktur von AsPh4 [V0C14] Nitrido and Oxochloro Complexes of Vanadium(V); the Crystal Structure of AsPh4[VOCl4]

“…Sie ist isotyp mit den analogen Tetraphenylarsonium-Salzen der Anionen MoOCLr [10], M0NCI4" [10], MoNBr4- [11], ReNCLr [12], OsNCL" [13] und RuNCLi" [14]. Darüber hinaus besteht eine enge strukturelle Verwandtschaft zu den in der gleichen Raumgruppe kristallisierenden Verbindungen AsPh4[AuCl4] [15] …”