25463-79-0Relevant academic research and scientific papers
[NBu4][ReNCl4]: Facile synthesis, structure, electron paramagnetic resonance spectroscopy and reactions
Abram, Ulrich,Braun, Martin,Abram, Sonja,Kirmse, Reinhard,Voigt, Andreas
, p. 231 - 238 (1998)
The compound [NBu4][ReNCl4] has been found to be easily accessible by the reaction of [NBu4][ReO4] with sodium azide and HCl gas in ethanol and represents an excellent precursor for the synthesis of further rhenium nitrido complexes. It has been studied by X-ray crystallography. Rhenium(VI) compounds of the general formula [ReNX4(5)]-,2- (X = Br or NCS) were obtained when [NBu4][ReNCl4] reacts with HBr or KSCN. The products as well as mixed-ligand intermediates which are formed during the ligand exchange have been studied by EPR spectroscopy. The EPR parameters of the individual mixed-ligand compounds are clearly correlated to the composition of the co-ordination sphere and can be used to characterize the mixed-ligand species unambiguously. This is shown by a nearly linear dependence of g0, g∥, a0Re and A∥Re on the spin-orbit coupling constants of the equatorial donors. Reactions of [NBu4][ReNCl4] with most organic ligands yielded rhenium(V) compounds. A number of phosphine complexes and chelates with sulfur-containing ligands have been prepared and spectroscopically characterized. A crystallographic study on [ReN(Hdetcb)2] (Hdetcb- = N2-diethylthiocarbamoylbenzamidinate) shows cis co-ordination for the chelating S,N-donor ligands. Weak intermolecular hydrogen bridges have been found between the co-ordinated nitrogen atoms and the lone pair of the nitrido nitrogen. A comparison between the crystal structural data of [NBu4]2[ReN(mnt)2] (mnt2- = 1,2-dicyanoethene-1,2-dithiolate), prepared from [NBu4][ReNCl4] and Na2mnt, and [NBu4][ReO(mnt)2] shows longer Re-S bonds in the nitrido anion but markedly higher O-Re-S bond angles indicating higher steric requirements of the oxo ligand compared with 'N3-'.
Synthesis, structure, and photolysis of isocyanato complexes of rhenium
Bonfada,Abram,Straehle
, p. 757 - 762 (2008/10/09)
The ReIII isocyanato complex Re(NCO)3(PMe2Ph)3 yields from the reaction of ReCl3(PMe2Ph)3 with an excess of NaOCN in EtOH. It crystallizes in the triclinic space group P1 with a = 991.8(6), b = 1180.7(6), c = 1348.8(5) pm, α = 89.85(1)°, β = 94.12(1), γ = 111.56(1)°, Z = 2. In the mononuclear complex with an octahedral coordination of the Re atoms the phosphine and isocyanato ligands exhibit a meridional arrangement. By using a deficient amount of NaOCN the mono isocyanato complex Re(NCO)Cl2(PMe2Ph)3 is formed, and part of the educt is transformed to its isomer [(Me2PhP)3Re(μ-Cl)3Re(PMe 2Ph)3]Cl3. The mono isocyanato complex forms monoclinic crystals with the space group P21/n and a = 1467.5(7), b = 1310.6(7), c = 1603.2(8) pm, β = 112.08(1)°, Z = 4. The isocyanato ligand is in trans position to a Cl atom, and the phosphine ligands are coordinated in a meridional arrangement. [(Me2PhP)3Re(μ-Cl)3Re(PMe 2Ph)3]Cl3·2 EtOH crystallizes in the hexagonal space group P63/m with a = 1332.6(2), c = 2300.1(7) pm, Z = 2. The dinuclear complex cation occupies with its center a special position with the symmetry C3h. Photolysis of Re(NCO)Cl2(PMe2Ph)3 results in the cleavage of the isocyanato ligand with release of CO and formation of the nitrido complex ReNCl2(PMe2Ph)3. The reaction of ReNCl2(PMe2Ph)3 with NaOCN affords the complex ReN(NCO)2(PMe2Ph)3. It crystallizes in the space group P21/n with a = 943.0(3), b = 2635.2(4), c = 1212.6(5) pm, β = 109.88(1)°, Z = 4. In this nitrido complex, like in the educt, the phosphine ligands form a meridional arrangement. The nitrido ligand is in trans position to an isocyanato group. The distance Re≡N is 165.9(6) pm. Johann Ambrosius Barth 1998.
Dichlorotrisnitridorhenium(V),ReNCl2(Me2PhP)3
Forsellini, E.,Casellato, U.,Graziani, R.,Magon, L.
, p. 3081 - 3083 (2007/10/02)
, C24H33Cl2NP3Re, Mr = 686, orthorhombic, space group Pcab, a = 16.673 (5), b = 16.754 (5), c = 19.200 (6) Angstroem, V = 5364 (3) Angstroem3, Dx = 1.70 Mg m-3 for Z = 8, μ = 4.7 mm-1 (MoKα).The structure was solved by standard methods from X-ray diffractometer intensities and refined by full-matrix least squares to a final R of 0.034 for 2816 observed reflexions.The Re atom is in a distorted octahedral-coordination geometry and the Re-N bond length is 1.660 (8) Angstroem.
