Pyridinyl- and phosphano-guanidino complexes of formula [(η⁶-p-cymene)OsCl(H₂L)][SbF₆] (cymene = MeC₆H₄iPr; H₂L = N,N′-bis(p-Tolyl)-N′′-(2-pyridinylmethyl)guanidine, H₂L1 (1) and N,N′-bis(p-Tolyl)-N′′-(2-diphenylphosphanoethyl)guanidine, H₂L2 (2)) have been prepared from the dimer [{(η⁶-p-cymene)OsCl}₂(μ-Cl)₂] and H₂L in the presence of NaSbF₆. Treatment of complex 2 with HCl renders the phosphano–guanidinium complex [(η⁶-p-cymene)OsCl₂(H₃L₂)][SbF₆] (3). Compounds 1 and 2 react with AgSbF₆ rendering the cationic aqua complexes [(η⁶-p-cymene)Os(H₂L)(OH₂)][SbF₆]₂ (H₂L = H₂L1 (4), H₂L2 (5)). Addition of monodentate ligands L to compound 4 affords complexes of formula [(η⁶-p-cymene)Os(H₂L1)L][SbF₆]₂ (L = py (6), 4-(NHMe)py (7), CO (8), P(OMe)₃ (9)). Treatment of complexes 4 and 5 with NaHCO₃ renders the monocationic complexes [(η⁶-p-cymene)Os(κ³N,N′,N′′-HL1)][SbF₆] (10) and [(η⁶-p-cymene)Os(κ³N,N′,P-HL2)][SbF₆] (11), respectively, in which the HL ligand adopts a fac-κ³ coordination mode. The new complexes have been characterised by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1–4, 6, 8, and 11, by X-ray diffractometric methods. The phosphano–guanidino complexes 2 and 5 exhibit a temperature dependent fluxional process in solution. The new 18 electron complexes 1, 2, 6, and 8–10 are active catalysts for the Friedel–Crafts reaction between trans-β-nitrostyrene and N-methyl-2-methylindole. Conversions greater than 90% were obtained. Proton NMR studies support a mechanism involving the Brønsted-acid activation of trans-β-nitrostyrene through the NH functionalities of the coordinated guanidine ligands.

中文翻译：

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含的胍配体的半三明治复合物

式的吡啶基和phosphano胍配合物[（η ⁶ - p -cymene）OSCL（ħ ₂大号）] [的SbF ₆ ]（对伞花烃=的MeC ₆ H ^ ₄的iPr; ħ ₂大号= Ñ，Ñ双（p -Tolyl）-N ''-（2-吡啶基甲基）胍，H ₂ L1（1）和N，N'-双（p -Tolyl）-N ''-（2-二苯基膦酰基乙基）胍，H ₂ L2（2））已经从二聚物制备[{（η ⁶ - p -cymene）OSCL} ₂（μ-Cl）的₂ ]和ħ ₂大号在NaSbF的存在₆。的复杂治疗2用HCl呈现phosphano-胍络合物[（η ⁶ - p -cymene）OSCL ₂（ħ ₃大号₂）] [的SbF ₆ ]（3）。化合物1和2与AgSbF反应₆呈现阳离子水性络合物[（η ⁶ - p -cymene）OS（H ₂ L）（OH ₂）] [SbF ₆ ] ₂（H ₂ L＝H ₂ L1（4），H ₂ L2（5））。单齿的另外配体大号至化合物4种的式，得到配合物[（η ⁶ - p -cymene）OS（ħ ₂ L1）大号] [的SbF ₆ ] ₂（大号= PY（6），4-（NHMe）PY（7），一氧化碳（8），P（OMe）₃（9））。复合物的治疗4和5用NaHCO ₃使该单阳离子配合物[（η ⁶ - p -cymene）OS（κ ³ Ñ，Ñ '，ñ '' - HL1）] [的SbF ₆ ]（10）和[（η ⁶ - p -cymene）OS（κ ³ ñ，ñ '，P - HL2）] [的SbF ₆ ]（11），分别在其中HL配体采用FAC -κ ³的协调模式。新的配合物已经被表征通过分析和光谱手段，包括确定化合物的晶体结构的1-4，6，8，和11，通过X射线衍射物的方法。膦-胍基配合物2和5在溶液中表现出温度依赖性的通量过程。新的18个电子复合物1，2，6，和8〜10是用于之间的Friedel-Crafts反应的活性催化剂的反式-β-硝基苯乙烯和Ñ-甲基-2-甲基吲哚。转化率大于90％。质子NMR研究支持一种机制，该机制涉及通过配位的胍配体的NH官能团反式-β-硝基苯乙烯的布朗斯台德酸活化。