81028-33-3Relevant academic research and scientific papers
Aryldiazenido, aryldiazene, and arylhydrazido complexes: Derivatives of dicarbonyl(η5-cyclopentadienyl)rhenium and the X-ray structure of [(η5-C5H5)Re(CO)2[p-NN(CH 3)C6H4OMe]]
Barrientos-Penna, Carlos F.,Einstein, Frederick W. B.,Jones, Terry,Sutton, Derek
, p. 2578 - 2585 (2008/10/08)
The aryldiazenido complexes [(η5-C5H5)Re(CO)2(N 2R)][BF4] (1: R = C6H4X with X = (a) p-Me, (b) p-OMe, (c) o-OMe, (d) p-NEt2, and (e) o-CF3; R = C6H3X2 with X2 = (f) 2,6-Me2 and (g) 3,5-Me2) have been synthesized from the reaction of the appropriate arenediazonium tetrafluoroborate with (η5-C5H5)Re(CO)2THF. They react with NaBH4 at N(1) to produce the corresponding aryldiazene complexes [(η5-C5H5)Re(CO)2(NHNR)] (3), which exhibit δ(NH) near 15 in the 1H NMR but react with MeLi at N(2) to yield the hydrazido(2-) derivatives [(η5-C5H5)Re(CO)2[NN(Me)R]] (6). An X-ray structure determination on 6b (R = p-C6H4OMe) shows it to contain a bent metal-hydrazido(2-) skeleton, with selected dimensions Re-N(I) = 1.937 (7) A?, N(1)-N(2) = 1.283 (10) A?, and Re-N(1)-N(2) = 138.1 (6)°. Compound 6b crystallizes from hexane as dark red solvent-free crystals in the space group P21/c of the monoclinic system with a = 5.895 (1) A?, b = 21.096 (4) A?, c = 12.829 (2) A?, β = 112.05 (1)°, and Z = 4. The calculated and measured densities are 2.055 and 2.02 (2) g cm-3, respectively. On the basis of 2178 observed, three-dimensional, X-ray-counter measured intensities with I > 2.3σ(I) in the range 3° ≤ 2θ ≤ 50° (Mo Kα), the structure was solved and refined by full-matrix, least-squares methods to R = 0.037 and Rw = 0.040. These hydrazido(2-) complexes can be protonated at N(1) with HBF4 to yield the hydrazido(1-) complexes [(η5-C5H5)Re(CO) 2[NHN(Me)R]][BF4] (8) with δ(NH) near 16. The aryldiazenido complexes also react with MeLi, PhLi, and n-BuLi to give monocarbonyl compounds formulated to be acyl or benzoyl derivatives, resulting from nucleophilic attack at one CO group.
