Franklin Brenton R, Herrick Richard S, Ziegler Christopher J, Cetin Anil, Barone Natalie, Condon Laura R
Department of Chemistry, College of the Holy Cross, Worcester, Massachusetts 01610, USA.
Inorg Chem. 2008 Jul 7;47(13):5902-9. doi: 10.1021/ic800363w. Epub 2008 May 28.
The reactions of ammonia, pyridine (py), N-methyl imidazole (N-MeIm), tetrahydrothiophene (tht), and piperidine (pip) with Re(CO) 3(H 2O) 3 (+), 1 ( + ), were investigated employing aqueous conditions under atmospheric dioxygen. The reaction of [ 1]Br in aqueous ammonia led to [Re(CO) 3(NH 3) 3]Br ([ 2]Br) as the only product isolated. For the aqueous reactions of [ 1]Br with py, N-MeIm, and tht, mixtures of products are formed because of competition between the bromide and added ligand, even when the ligand is present in excess. Substitution of the PF 6 (-) anion for Br (-) leads to the clean formation of [Re(CO) 3L 3][PF 6] ([ 3][PF 6]-[ 5][PF 6]) for py, N-MeIm, and tht, respectively, as the only products observed. Reaction of [ 1][PF 6] with pip produces the dimeric species, (pip)(CO) 3Re(micro-OH) 2Re(CO) 3(pip), 6. Reactions of [ 1]Br were also performed in methanol for comparison purposes. The reaction with pip in this solvent led to the analogous dimer, (pip)(CO) 3Re(micro-OMe) 2Re(CO) 3(pip), 7; however, reactions with py, N-MeIm, and tht gave Re(CO) 3L 2Br, 8- 10, respectively, as the only products. The crystal structures of compounds [ 2]Br- 10 are reported.
在大气氧存在的水相条件下，研究了氨、吡啶（py）、N - 甲基咪唑（N - MeIm）、四氢噻吩（tht）和哌啶（pip）与三羰基铼三水合物阳离子（Re(CO)₃(H₂O)₃⁺，1⁺）的反应。[1]Br在氨水中反应生成[三羰基铼三氨合物]溴（[Re(CO)₃(NH₃)₃]Br，[2]Br），这是唯一分离得到的产物。对于[1]Br与py、N - MeIm和tht的水相反应，由于溴离子与添加配体之间的竞争，即使配体过量，也会形成产物混合物。用PF₆⁻阴离子取代Br⁻，分别得到[三羰基铼三（吡啶）合物]六氟磷酸（[Re(CO)₃L₃][PF₆]，[3][PF₆] - [5][PF₆]），其中L分别为py、N - MeIm和tht，这是仅观察到的产物。[1][PF₆]与pip反应生成二聚体物种（pip）(CO)₃Re(μ - OH)₂Re(CO)₃(pip)，6。为作比较，[1]Br的反应也在甲醇中进行。在该溶剂中与pip反应生成类似的二聚体（pip）(CO)₃Re(μ - OMe)₂Re(CO)₃(pip)，7；然而，与py、N - MeIm和tht反应分别得到Re(CO)₃L₂Br，8 - 10，作为唯一产物。报道了化合物[
