Synthesis and Reactivity of Hybrid Phosphido- and Hydrosulfido-Bridged Diruthenium Complexes: Transformations into Diruthenium and Tetraruthenium Complexes Bridged by Phosphido and Sulfido Ligands

Miyake, Yoshihiro; Moriyama, Taichi; Tanabe, Yasuhiro; Endo, Satoshi; Nishibayashi, Yoshiaki

doi:10.1021/om3001247

Cited by 8 publications

(1 citation statement)

References 67 publications

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“…The bdt ligand binds to the two ruthenium centers in a μ-η 2 :η 2 fashion, and the chloride is located at a symmetrical position with respect to the Ru–Ru vector. The Ru1–Cl1 and Ru2–Cl1 distances are 2.205(6) and 2.377(2) Å, respectively, which are shorter than the distance between the ruthenium center and terminal chloride in the reported diruthenium complexes (2.40–2.44 Å), but in the range of the chloride bridged diruthenium complexes . Two Cp* ligands coordinate to the two Ru centers with their C 5 planes perpendicular to the Ru–Ru vector, and the dihedral angle between the two Cp* rings is 25.48(27)°.…”

Section: Resultsmentioning

confidence: 85%

C–H Activation of Cp* Ligand Coordinated to Ruthenium Center: Synthesis and Reactivity of a Thiolate-Bridged Diruthenium Complex Featuring Fulvene-like Cp* Ligand

Yang

Tong

et al. 2017

Organometallics

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In the presence of weak base Et 3 N, the interaction of [Cp*Ru(μ-η 2 :η 4 -bdt)RuCp*] (1, Cp* = η 5 -C 5 Me 5 ; bdt = benzene-1,2-dithiolate) with 2 equiv of Fc•PF 6 resulted in facile C−H activation of one methyl group in coordinated Cp* to give a diruthenium complex with a fulvene-like Cp* ligand, [(η 5 :η 1 -C 5 Me 4 CH 2 )Ru(μ-η 2 :η 4 -bdt)RuCp*][PF 6 ] (2[PF 6 ]), in which the fulvene-like Cp* moiety is best described as an η 5 :η 1 -tetramethylfulvene ligand based on 1 H NMR and 13 C NMR spectroscopic data. When complex 2[PF 6 ] 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(μ-η 2 :η 2 -bdt)(μ-Cl)RuCp*][PF 6 ] (3[PF 6 ]). While complex 2[PF 6 ] reacted with iodine, functionalization of a Cp* methyl group was realized to give a Cp* ring iodine-substituted complex [(η 5 -C 5 Me 4 CH 2 I)Ru(t-I)(μ-η 2 :η 4 -bdt)RuCp*][PF 6 ] (4[PF 6 ]) in excellent yield. Importantly, reaction of 2[PF 6 ] with elemental sulfur led to the S−S bond fission of S 8 following insertion of a disulfide fragment into the Ru−methylene bond to produce [(η 5 :η 1 -C 5 Me 4 CH 2 S 2 )Ru(μ-η 2 :η 4 -bdt)RuCp*][PF 6 ] (5[PF 6 ]), which provides strong chemical evidence for structural description of the fulvene-like Cp* ligand in 2[PF 6 ]. Most strikingly, treatment of 2[PF 6 ] with CO and t BuNC resulted in the coordination mode switch of the fulvene-like Cp* ligand from η 5 :η 1 on one ruthenium center to μ-η 5 :η 1 between two ruthenium centers to afford [Ru(μ-η 5 :η 1 -C 5 Me 4 CH 2 )(t-CO)(μ-η 2 :η 2 -bdt)RuCp*][PF 6 ] (6[PF 6 ]) and [Ru(μ-η 5 :η 1 -C 5 Me 4 CH 2 )(t-t BuNC)(μ-η 2 :η 2 -bdt)RuCp*][PF 6 ] (7[PF 6 ]), respectively.

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Section: Resultsmentioning

confidence: 85%