Albertin Gabriele, Antoniutti Stefano, Bacchi Alessia, D'Este Claudia, Pelizzi Giancarlo
Dipartimento di Chimica, Università Ca' Foscari di Venezia, Dorsoduro 2137, 30123 Venezia, Italy.
Inorg Chem. 2004 Feb 23;43(4):1336-49. doi: 10.1021/ic034820z.
Chloro complexes [RuCl(N-N)P3]BPh4 (1-3) [N-N = 2,2'-bipyridine, bpy; 1,10-phenanthroline, phen; 5,5'-dimethyl-2,2'-bipyridine, 5,5'-Me2bpy; P = P(OEt)3, PPh(OEt)2 and PPh2OEt] were prepared by allowing the [RuCl4(N-N)].H2O compounds to react with an excess of phosphite in ethanol. The bis(bipyridine) [RuCl(bpy)2[P(OEt)3]]BPh4 (7) complex was also prepared by reacting RuCl2(bpy)2.2H2O with phosphite and ethanol. Treatment of the chloro complexes 1-3 and 7 with NaBH4 yielded the hydride [RuH(N-N)P3]BPh4 (4-6) and [RuH(bpy)2P]BPh4 (8) derivatives, which were characterized spectroscopically and by the X-ray crystal structure determination of [RuH(bpy)[P(OEt)3]3]BPh4 (4a). Protonation reaction of the new hydrides with Brønsted acid was studied and led to dicationic [Ru(eta2-H2)(N-N)P3]2+ (9, 10) and [Ru(eta(2-H2)(bpy)2P]2+ (11) dihydrogen derivatives. The presence of the eta2-H2 ligand was indicated by a short T(1 min) value and by the measurements of the J(HD) in the Ru isotopomers. From T(1 min) and J(HD) values the H-H distances of the dihydrogen complexes were also calculated. A series of ruthenium complexes, RuL(N-N)P32 and RuL(bpy)2P2 (P = P(OEt)3; L = H2O, CO, 4-CH3C6H4NC, CH3CN, 4-CH3C6H4CN, PPh(OEt)2], was prepared by substituting the labile eta2-H2 ligand in the 9, 10, 11 derivatives. The reactions of the new hydrides 4-6 and 8 with both mono- and bis(aryldiazonium) cations were studied and led to aryldiazene Ru(C6H5N=NH)(N-N)P32 (19, 21), [Ru(N-N)P3]2(mu-4,4'-NH=NC6H4-C6H4N=NH)4 (20), and Ru(C6H5N=NH)(bpy)2P2 (22) derivatives. Also the heteroallenes CO2 and CS2 reacted with [RuH(bpy)2P]BPh4, yielding the formato [Rueta1-OC(H)=O2P]BPh4 and dithioformato [Rueta1-SC(H)=S2P]BPh4 derivatives.
通过使[RuCl₄(N-N)].H₂O化合物与过量的亚磷酸酯在乙醇中反应，制备了氯配合物[RuCl(N-N)P₃]BPh₄（1 - 3）[N-N = 2,2'-联吡啶，bpy；1,10-菲咯啉，phen；5,5'-二甲基-2,2'-联吡啶，5,5'-Me₂bpy；P = P(OEt)₃、PPh(OEt)₂和PPh₂OEt]。双（联吡啶）[RuCl(bpy)₂[P(OEt)₃]]BPh₄（7）配合物也通过使RuCl₂(bpy)₂·2H₂O与亚磷酸酯和乙醇反应制备。用NaBH₄处理氯配合物1 - 3和7，得到氢化物[RuH(N-N)P₃]BPh₄（4 - 6）和[RuH(bpy)₂P]BPh₄（8）衍生物，通过光谱表征以及对[RuH(bpy)[P(OEt)₃]₃]BPh₄（4a）进行X射线晶体结构测定进行表征。研究了新氢化物与布朗斯特酸的质子化反应，得到二价阳离子[Ru(η²-H₂)(N-N)P₃]²⁺（9, 10）和[Ru(η²-H₂)(bpy)₂P]²⁺（11）二氢衍生物。通过短的T(1 min)值以及对Ru同位素异构体中J(HD)的测量表明存在η²-H₂配体。根据T(1 min)和J(HD)值还计算了二氢配合物的H - H距离。通过取代9、10、11衍生物中不稳定的η²-H₂配体，制备了一系列钌配合物RuL(N-N)P₃₂和RuL(bpy)₂P₂（P = P(OEt)₃；L = H₂O、CO、4-CH₃C₆H₄NC、CH₃CN、4-CH₃C₆H₄CN、PPh(OEt)₂]。研究了新氢化物4 - 6和8与单芳基重氮阳离子和双芳基重氮阳离子的反应，得到芳基二氮烯Ru(C₆H₅N=NH)(N-N)P₃₂（19, 21）、[Ru(N-N)P₃]₂(μ-4,4'-NH=NC₆H₄-C₆H₄N=NH)₄（20）和Ru(C₆H₅N=NH)(bpy)₂P₂（22）衍生物。此外，异双烯CO₂和CS₂与[RuH(bpy)₂P]BPh₄反应，生成甲酰基[Ruη¹-OC(H)=O₂P]BPh₄和二硫代甲酰基[Ruη¹-SC(H)=S₂P]BPh₄衍生物。
