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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kl?ui's oxygen tripodal ligand
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Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kl?ui's oxygen tripodal ligand

机译:含钾氟三脚架配体的钌亚硝酰基配合物的合成,结构和反应性

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Ruthenium nitrosyl complexes containing the Kl?ui's oxgyen tripodal ligand L_(OEt)~- ([CpCo{P(O)(OEt)_2} _3]~- where Cp = η~5-C_5H _5) were synthesized and their photolysis studied. The treatment of [Ru(NN)(NO)Cl_3] with [AgL_(OEt)] and Ag(OTf) afforded [L _(OEt)Ru(NN)(NO)][OTf]_2 where NN = 4,4′-di-tert-butyl- 2,2′-bipyridyl (dtbpy) (2·[OTf]_2), 2,2′-bipyridyl (bpy) (3·[OTf]_2), N,N,N′N′- tetramethylethylenediamine (4·[OTf]_2). Anion metathesis of 3·[OTf]_2 with HPF_6 and HBF_4 gave 3·[PF_6]_2 and 3·[BF_4]_2, respectively. Similarly, the PF6- salt 4·[PF _6]_2 was prepared by the reaction of 4·[OTf] _2 with HPF_6. The irradiation of [L_(OEt)Ru(NO) Cl_2] (1) with UV light in CH_2Cl_2-MeCN and tetrahydrofuran (thf)-H_2O afforded [L_(OEt)RuCl _2(MeCN)] (5) and the chloro-bridged dimer [L_(OEt)RuCl] _2(μ-Cl)_2 (6), respectively. The photolysis of complex [2][OTf]_2 in MeCN gave [L_(OEt)Ru(dtbpy)(MeCN)][OTf] _2 (7). Refluxing complex 5 with RNH2 in thf gave [L _(OEt)RuCl_2(NH_2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl_2 gave [L OEtRuCl_3] (11), whereas the reduction of complex 6 with Zn and NH_4PF_6 in MeCN yielded [L_(OEt)Ru(MeCN) _3][PF_6] (12). The reaction of 3·[BF _4]_2 with benzylamine afforded the μ-dinitrogen complex [{L_(OEt)Ru(bpy)}_2(μ-N_2)][BF_4] _2 (13) that was oxidized by [Cp_2Fe]PF_6 to a mixed valence RuII,III species. The formal potentials of the RuL _(OEt) complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.
机译:合成了含有Kluui's oxgyen三脚架配体L_(OEt)〜-([CpCo {P(O(OE)_2} _3]〜-其中Cp =η〜5-C_5H _5)的钌亚硝酰基配合物。用[AgL_(OEt)]和Ag(OTf)处理[Ru(NN)(NO)Cl_3]得到[L _(OEt)Ru(NN)(NO)] [OTf] _2,其中NN = 4,4 ′-二叔丁基-2,2'-联吡啶(dtbpy)(2·[OTf] _2),2,2′-联吡啶(bpy)(3·[OTf] _2),N,N,N' N'-四甲基乙二胺(4·[OTf] _2)。 HPF_6和HBF_4对3·[OTf] _2进行的阴离子复分解反应分别得到3·[PF_6] _2和3·[BF_4] _2。类似地,通过4·[OTf] _2与HPF_6的反应制备了PF6-盐4·[PF _6] _2。在CH_2Cl_2-MeCN和四氢呋喃(thf)-H_2O中用紫外光照射[L_(OEt)Ru(NO)Cl_2](1),得到[L_(OEt)RuCl _2(MeCN)](5)和氯代-桥接二聚体[L_(OEt)RuCl] _2(μ-Cl)_2(6)。复杂的[2] [OTf] _2在MeCN中的光解得到[L_(OEt)Ru(dtbpy)(MeCN)] [OTf] _2(7)。将具有RNH 2的络合物5回流,得到[L _(OEt)RuCl_2(NH_2R)](R = tBu(8),对甲苯基(9),Ph(10))。配合物6用PhICl_2氧化得到[L OEtRuCl_3](11),而配合物6在MeCN中用Zn和NH_4PF_6还原得到[L_(OEt)Ru(MeCN)_3] [PF_6](12)。 3·[BF _4] _2与苄胺的反应生成了被[Cp_2Fe]氧化的μ-二氮配合物[{L_(OEt)Ru(bpy)} _ 2(μ-N_2)] [BF_4] _2(13) PF_6为混合价RuII,III物种。 RuL_(OEt)配合物的形式势已通过循环伏安法测定。配合物5、6、10、11和13的结构已经通过X射线晶体学确定。

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