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论文类型：期刊论文

发表时间：2017-04-24

发表刊物：ORGANOMETALLICS

收录刊物：SCIE、EI、Scopus

卷号：36

期号：8

页面范围：1515-1521

ISSN号：0276-7333

摘要：In the presence of weak base Et3N, the interaction of [Cp*Ru(mu-eta(2):eta(4)-bdt)RuCp*] (1, Cp* = eta(5)- C5Me5; bdt = benzene-1,2-dithiolate) with 2 equiv of Fc center dot PF6 resulted in facile CH activation of one methyl group in coordinated Cp* to give a diruthenium complex with a fulvene-like Cp* ligand, [(eta(5):eta(1)-C5Me4CH(2))Ru(mu-eta(2):eta(4)-bdt)RuCp*][PF6] (2[PF6]), in which the fulvene-like Cp* moiety is best described as an eta(5):eta(1)-tetramethylfulvene ligand based on H-1 NMR and C-13 NMR spectroscopic data. When complex 2[PF6] was subjected to the electrophilic attack of HCl, an intact Cp* group was regenerated from the fulvene-like Cp* ligand along with the formation of the chloride bridged complex [Cp*Ru(mu-eta(2):eta(2)-bdt)(mu-Cl)RuCp*][PF6] (3[PF6]). While complex 2[PF6] reacted with iodine, functionalization of a Cp* methyl group was realized to give a Cp* ring iodine-substituted complex [(eta(5)-C5Me4CH2I)Ru(t-I)(mu-eta(2):eta(4)-bdt)RuCp*][PF6] (4[PF6]) in excellent yield. Importantly, reaction of 2[PF6] with elemental sulfur led to the SS bond fission of S8 following insertion of a disulfide fragment into the Rumethylene bond to produce [(eta(5):eta(1)-C5Me4CH2S2)Ru(mu-eta(2):eta(4)-bdt)RuCp*][PF6] (5[PF6]), which provides strong chemical evidence for structural description of the fulvene-like Cp* ligand in 2[PF6]. Most strikingly, treatment of 2[PF6] with CO and (BuNC)-Bu-t resulted in the coordination mode switch of the fulvene-like Cp* ligand from eta(5):eta(1) on one ruthenium center to mu-eta(5):eta(1) between two ruthenium centers to afford [Ru(mu-eta(5):eta(1)-C5Me4CH2)(t-CO)(mu-eta(2):eta(2)-bdt)RuCp*][PF6] (6[PF6]) and [Ru(mu-eta(5):eta(1)-C5Me4CH2)(t-(BuNC)-Bu-t)(mu-eta(2):eta(2)-bdt)RuCp*][PF6] (7[PF6]), respectively.