ARENE RUTHENIUM(II) COMPLEXES FORMED BY DEHYDROGENATION OF CYCLOHEXADIENES WITH RUTHENIUM(III) TRICHLORIDE
ARENE RUTHENIUM(II) COMPLEXES FORMED BY DEHYDROGENATION OF CYCLOHEXADIENES WITH RUTHENIUM(III) TRICHLORIDE
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DOI：
10.1039/dt9740000233
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发表时间：
1974-01-01
期刊：
影响因子：
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通讯作者：
SMITH, AK
中科院分区：
文献类型：
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作者：
BENNETT, MA;SMITH, AK
通过适当的环己-1，3-二烯或环己-1，4-二烯与三氯化Ru(III)的脱氢反应，合成了芳二氯Ru配合物[RuCl2(芳烃)]2。它们与配体(L)如吡啶、叔膦或叔基精氨酸反应生成单体络合物[RuCl2(芳烃)L]，形式上类似于芳基三羰基铬络合物。还制备了类似的二溴、二碘、卤代(甲基)和二甲基衍生物；后者是热不稳定的，对空气敏感。配合物[RuCl2(芳烃)]2(芳烃=苯或对伞花烃)与水反应生成双核三氯阳离子物种[Ru2C13(芳烃)2]+，与四氟硼酸银在乙腈中反应生成单体[Ru(芳烃)(MeCN)3]2+。红外线。和n.m.r。给出了新复合体的数据。配合物[RuCl2(芳烃)L](L=PbUN_3或PPh_3)在加热或紫外光下发生部分或全部芳烃交换。在芳香族溶剂中辐射，配位的对伞花烃最容易被取代。该交换方法可用于制备六甲基苯络合物，如[RuCl2(C6Me6)(Pbun3)]。计算结果与已有的芳烃交换数据进行了比较，并从电子和空间位阻对金属-芳烃成键的影响进行了讨论。
Arenedi-µ-chloro-ruthenium complexes [RuCl2(arene)]2 have been prepared by dehydrogenation of the appropriate cyclohexa-1,3-diene or cyclohexa-1,4-diene with ethanolic ruthenium(III) trichloride. They react with ligands (L) such as pyridine, tertiary phosphines, or tertiary arsines to give monomeric complexes [RuCl2(arene)L], which are formally analogous to the arenetricarbonylchromium complexes. Analogous dibromo-, di-iodo-, halogeno-(methyl), and dimethyl derivatives have also been prepared; the latter are thermally unstable and air-sensitive. Reaction of the complexes [RuCl2(arene)]2(arene = benzene or p-cymene) with water gives binuclear tri-µ-chloro-cationic species [Ru2C13(arene)2]+, and reaction with silver(I) tetrafluoroborate in acetonitrile gives monomeric [Ru(arene)(MeCN)3]2+. I.r. and n.m.r. data for the new complexes are given. The complexes [RuCl2(arene)L](L = PBun3 or PPh3) undergo partial or complete arene exchange on heating or on u.v. irradiation in an aromatic solvent, co-ordinated p-cymene being the most easily displaced. The exchange method can be used to prepare hexamethylbenzene complexes, e.g.[RuCl2(C6Me6)(PBun3)]. The results are compared with available data on arene exchange in arenetricarbonylchromium complexes and discussed in terms of electronic and steric effects on metal–arene bonding.