Albertin Gabriele, Antoniutti Stefano, Bedin Marco, Castro Jesús, Garcia-Fontan Soledad
Dipartimento di Chimica, Università Ca' Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy.
Inorg Chem. 2006 May 1;45(9):3816-25. doi: 10.1021/ic052063u.
Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.
通过使三氟甲磺酸盐[M(κ²-OTf)P₄]OTf物种首先与1,3-ArN=NN(H)Ar三氮烯反应，然后与过量的三乙胺反应，制备了三氮烯化物[M(η²-1,3-ArNNNAr)P₄]BPh₄[M = Ru, Os; Ar = Ph, 对甲苯基; P = P(OMe)₃, P(OEt)₃, PPh(OEt)₂]配合物。或者，通过使氢化物[RuH(η²-H₂)P₄]⁺和RuH(κ¹-OTf)P₄化合物与1,3-二芳基三氮烯反应，获得钌三氮烯化物[Ru(η²-1,3-ArNNNAr)P₄]BPh₄衍生物。通过对[Ru(η²-1,3-PhNNNPh){P(OEt)₃}₄]BPh₄衍生物进行光谱学和X射线晶体学表征对这些配合物进行了表征。通过使κ¹-三氟甲磺酸盐MH(κ¹-OTf)P₄与1,3-二芳基三氮烯反应，制备了氢化物三氮烯[OsH(η¹-1,3-ArN=NN(H)Ar)P₄]BPh₄[P = P(OEt)₃, PPh(OEt)₂; Ar = Ph, 对甲苯基]和[RuH{η¹-1,3-对甲苯基-N=NN(H)-对甲苯基}{PPh(OEt)₂}₄]BPh₄衍生物。还获得了[Os(κ¹-OTf){η¹-1,3-PhN=NN(H)Ph}{P(OEt)₃}₄]BPh₄中间体。使用由1,3-Ph¹⁵N=N¹⁵N(H)Ph配体制备的¹⁵N标记的三氮烯配合物进行了变温NMR研究。锇二氢化物[OsH(η²-H₂)P₄]BPh₄配合物[P = P(OEt)₃, PPh(OEt)₂]与1,3-ArN=NN(H)Ar三氮烯反应，生成氢化物-二氮烯[OsH(ArN=NH)P₄]BPh₄衍生物。报道了[OsH(PhN=NH){PPh(OEt)₂}₄]BPh₄配合物的X射线晶体结构测定。还报道了一条解释二氮烯配合物形成的反应路径。
