Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
Dalton Trans. 2013 Sep 28;42(36):13126-36. doi: 10.1039/c3dt51557e. Epub 2013 Jul 24.
A synthetic route to C(4/5)-bis(phosphinoyl)imidazole-2-thiones (7d,e) (d: R(1) = (n)Bu, R(2) = Me; e: R(1) = n-dodecyl, R(2) = Me) and C(4/5)-bis(thio/selenophosphinoyl)imidazole-2-thiones (8b,c), (9a,b,e) and 10a (a: R(1) = R(2) = Me; b: R(1) = R(2) = Ph, c: R(1) = (i)Pr, R(2) = Me) is presented that employs initial C(5) lithiation of mono-phosphinoyl/thiophosphinoyl substituted imidazole-2-thiones (3c-e)/(4a-c,e) followed by reaction with chlorodiphenylphosphane, leading to mixed phosphinoyl and phosphanyl substituted imidazole-2-thiones (5c-e) or mixed thiophosphinoyl and phosphanyl substituted imidazole-2-thiones (6a-c,e). Subsequent oxidation of mixed phosphinoyl and phosphanyl substituted imidazole-2-thione (5d,e) with H2O2-urea gives the bis(phosphinoyl) substituted imidazole-2-thiones (7d,e), and the oxidation of mixed thiophosphinoyl and phosphanyl substituted imidazole-2-thione (6a-c,e) using H2O2-urea, elemental sulfur or elemental selenium gives a set of mixed P(V)-chalcogenide substituted imidazole-2-thiones (8b,c), (9a,b,e) and 10a, respectively. P(V,V) substituted imidazole-2-thiones 7d and 9a reacted with tellurium tetrachloride, titanium tetrachloride or palladium dichloride to give complexes 11d, (12d and 12d') and 14a, respectively, having a bidentate chelate (11d and 14a) or a monodentate bonding motif (12d,d'). The titanium complexes 12d,d' slowly and selectively converted into the mono-ethoxy substituted product 13 possessing a seven membered chelate motif being unprecedented in the titanium chemistry of phosphine oxide donor ligands. The compounds were characterized by elemental analyses, spectroscopic and spectrometric methods and, in addition, X-ray diffraction studies in the case of 5c, 7d, 8b, 9a and 13.
一种合成 C(4/5)-双(膦酰基)咪唑-2-硫酮（7d，e）（d：R(1) = (n)Bu，R(2) = Me；e：R(1) = n-十二烷基，R(2) = Me）和 C(4/5)-双（硫代/硒代膦酰基）咪唑-2-硫酮（8b，c）、（9a，b，e）和 10a（a：R(1) = R(2) = Me；b：R(1) = R(2) = Ph，c：R(1) = (i)Pr，R(2) = Me）的路线，该路线采用单膦酰基/硫代膦酰基取代的咪唑-2-硫酮（3c-e）/（4a-c，e）的初始 C(5)锂化，然后与二氯二苯基膦反应，得到混合膦酰基和膦基取代的咪唑-2-硫酮（5c-e）或混合硫代膦酰基和膦基取代的咪唑-2-硫酮（6a-c，e）。随后用 H2O2-尿素氧化混合膦酰基和膦基取代的咪唑-2-硫酮（5d，e）得到双（膦酰基）取代的咪唑-2-硫酮（7d，e），用 H2O2-尿素、元素硫或元素硒氧化混合硫代膦酰基和膦基取代的咪唑-2-硫酮（6a-c，e）分别得到一组混合 P(V)-杂原子取代的咪唑-2-硫酮（8b，c）、（9a，b，e）和 10a。P(V，V)取代的咪唑-2-硫酮 7d 和 9a 与四氯化碲、四氯化钛或二氯化钯反应，分别得到配合物 11d、（12d 和 12d'）和 14a，它们具有双齿螯合（11d 和 14a）或单齿键合模式（12d，d'）。钛配合物 12d，d' 缓慢且选择性地转化为具有七元螯合模式的单乙氧基取代产物 13，这在磷氧化物供体配体的钛化学中是前所未有的。这些化合物通过元素分析、光谱和光谱学方法进行了表征，此外，在 5c、7d、8b、9a 和 13 的情况下还进行了 X 射线衍射研究。
