Elektronenreiche Ruthenium-Thiolat-Komplexe, Synthese und Reaktionen mit Elektrophilen / Electron-Rich Ruthenium Thiolate Complexes, Synthesis and Reactions with Electrophiles

Abstract

Ruthenium thiolates [cpRu(PR′3)2(SR)] (PR′3 = PPh3,1/2 dppe, 1/2 dppm, R = Me, CH2Ph) are obtained from the corresponding chlorides and NaSR. PPh3 is readily exchanged for CO to give the chiral complexes [cpRu(PPh3)(CO)(SR)]. Alkylation with methyl tosylate yields the cations [cpRu(dppe)(SMeR)]+ and [cpRu(PPh3)(CO)(SMeR)]+, which were isolated as their PF6- salts. The neutral carbonyls add dimethyl acetylenedicarboxylate giving five-membered metallocycles.

Half-sandwich ruthenium complexes of pentafluorobenzenethiolato ligands

“…Cyclopentadienyl ruthenium thiolate complexes containing phosphine ligands are known in the literature [8][9][10][11][12][13][14][15]. They have been made by metathesis reactions of the corresponding chlorides with a variety of thiolate donors [8][9][10][11].…”

“…They have been made by metathesis reactions of the corresponding chlorides with a variety of thiolate donors [8][9][10][11]. The complexes CpRu(PPh 3 ) 2 SR are made by refluxing CpRu(PPh 3 ) 2 Cl and thiolate anions for short times [8,9].…”

“…They have been made by metathesis reactions of the corresponding chlorides with a variety of thiolate donors [8][9][10][11]. The complexes CpRu(PPh 3 ) 2 SR are made by refluxing CpRu(PPh 3 ) 2 Cl and thiolate anions for short times [8,9]. The reactions of these complexes with two-electron donor ligands, L (L = CO, PR 3 , P(OR) 3 ), produced either the mono-(CpRu(PPh 3 )(L)SR) or the di-substituted complexes (CpRu(L) 2 SR) [10][11][12].…”

“…Heating the thiolate complexes in high boiling solvents (such as toluene) led to trimers of the formula [CpRuSR] 3 [18]. Alkylation or protonation of these thiolate complexes produced the thioether [CpRu(PPh 3 ) 2 SR 2 ] + or the thiol complexes [CpRu(PPh 3 ) 2 -(HSR)] + , respectively [8,17]. Similarly, the carbonylphosphine thiolates CpRu(PPh 3 )(CO)SR can be alkylated or protonated to give the corresponding thioether or thiol complexes [8,17].…”

“…Alkylation or protonation of these thiolate complexes produced the thioether [CpRu(PPh 3 ) 2 SR 2 ] + or the thiol complexes [CpRu(PPh 3 ) 2 -(HSR)] + , respectively [8,17]. Similarly, the carbonylphosphine thiolates CpRu(PPh 3 )(CO)SR can be alkylated or protonated to give the corresponding thioether or thiol complexes [8,17]. However, these carbonyl-phosphine thiolates react with nitrosonium salt to give the disulfidebridged complexes {(l-RSSR)[CpRu(PPh 3 )(CO)] 2 } 2+ .…”