Pentamethylcyclopentadienyl Ruthenium Complexes with Sulfur- and Selenium-Donor Ligands

Abstract

Treatment of [Cp*Ru(NO)Cl 2 ] (Cp* ) η 5 -C 5 Me 5 ) with NaQAr or LiQAr (Q ) S, Se, Te; Ar ) C 6 F 4 H or Ph) affords [Cp*Ru(NO)(QAr) 2 ]. Interactions of [Cp*Ru(NO)(SC 6 F 4 H) 2 ] with PR 3 (R ) Ph or Me) give [Cp*Ru(PR 3 ) 2 (SC 6 F 4 H)] via phosphoraminate intermediates. The crystal structures of [Cp*Ru(NO)(SC 6 F 4 H) 2 ] and [Cp*Ru(PMe 3 ) 2 (SC 6 F 4 H)] have been determined. Treatment of [Cp*Ru(MeCN) 3 ][PF 6 ] with HN[SeP(i-Pr) 2 ] 2 affords a novel Cp*Ru(IV) complex, [Cp*Ru{η 2 -Se 2 P(i-Pr) 2 }{η 2 -SeP(i-Pr) 2 }][PF 6 ], which has been characterized by X-ray crystallography.

Palladium and half sandwich ruthenium(II) complexes of selenated and tellurated benzotriazoles: Synthesis, structural aspects and catalytic applications

“…The 3 is another example of such Ru-selenoether complex. The Ru-C distances 6 ] the Ru-Se bond lengths [42] are reported in the range 2.538(2)-2.590(2) Å, longer than that of cation of 3 due to steric crowding. The Ru-Se bond distance found in bimetallic species [RuCp(CO)(C"CPh)(l-Se)ZrCp 2 ] 2.494(1) Å [43], is closer to that of cation of 3.…”

Half sandwich complexes of Ru(II) and complexes of Pd(II) and Pt(II) with seleno and thio derivatives of pyrrolidine: Synthesis, structure and applications as catalysts for organic reactions

“…(l 3 -S)(CO) 7 (l-dppm)][40]. For Ru(IV) complex [Cp * Ru{g 2 -Se 2 P (i-Pr) 2 }{g 2 -SeP(i-Pr)2 }][PF6 ] the Ru-Se bond lengths[41] are reported in the range 2.538(2)-2.590(2) Å, longer than those of 3 and 4 due to steric crowding. The Ru-Se and Ru-N (L1) bond distances of 6 (2.4770(5) and 2.190(3) Å, respectively) are somewhat shorter than those of 3/4.…”

Influence of Cyclopentadienyl Ring‐Tilt on Electron‐Transfer Reactions: Redox‐Induced Reactivity of Strained [2] and [3]Ruthenocenophanes

“…The α angle for species 15 was found to be 38.77°, an increase from the angle in precursor 5 [ α =29.6(5)°], but a decrease compared to that observed in dimer 8 [ α = 48.18(18)°, 48.83(10)°], suggesting that the steric strain associated with the formation of the RuRu bond in 8 increases the tilt angle. The RuS bond length (2.4107 Å) in 15 is similar to that in related species,51 and the phenyl ring is positioned about 90° with respect to the dicarba‐bridge CC bond, presumably to minimize steric repulsion with the Cp rings.…”