Relative stability of η5-cyclopentadienyl(olefin)ruthenium cations: The first estimation of the nature of the RuII-olefin bond

Ohkita, Kumakazu; Toshikazu, Hirao; Ikeda, Isao

doi:10.1016/0022-328x(94)80166-5

Cited by 15 publications

(16 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A low-spin, d 6 -cationic complex of a second-row late transition element offers the best probability to fulfill this requirement. We 22 and others 24,26 found previously that neither thioethers nor sulfoxides dissociate readily from 18electron complexes of the type described here. Nevertheless, the presence of a strong oxidant in the reaction mixture could lead to the formation of 17-electron intermediates which might then undergo rapid ligand exchange, possibly even in a catalytic cycle.…”

Section: Discussionsupporting

confidence: 43%

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹

et al. 1997

View full text Add to dashboard Cite

Ionic ruthenium thioether complexes [Cp(LL')Ru(SRR')]PF(6) (LL' = Ph(2)PCH(2)PPh(2) (1), Ph(2)PC(2)H(4)PPh(2) (2), (Ph(3)P, CO) (3), Me(2)PC(2)H(4)PPh(2) (4), (S,S)-Ph(2)PCHMeCHMePPh(2) (5), SRR' = MeSPh (a), MeS-i-Pr (b), MeSBz (c), i-PrSBz (d), EtSBz (e), MeSCy (f), SC(4)H(8) (g)) were synthesized from the corresponding chloro complexes [Cp(LL')RuCl] and thioethers. 5a crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 11.269(3) Å, b = 15.104(2) Å, c = 23.177(4) Å, and Z = 4. 5b crystallized in the monoclinic system, space group P2(1) (No. 4), with a = 10.539(5) Å, b = 16.216(9) Å, c = 11.011(8) Å, beta = 106.04(2) degrees, and Z = 2. A similar ligand exchange reaction yielded the analogous sulfoxide complexes [Cp(LL')Ru(S(O)RR')]PF(6) (6-10). 10a crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 14.1664(13) Å, b = 15.792(2) Å, c = 17.641(2) Å, and Z = 4. 10b.0.93CH(2)Cl(2) crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 12.069(2) Å, b = 17.379(2) Å, c = 19.760(5) Å, and Z = 4. The thioether complexes can also be directly converted to sulfoxide complexes with the strong oxygen transfer reagent dimethyldioxirane (DMD). No crossover products are formed when mixtures of two thioether complexes (e.g., 1a/2c or 1c/2a) are treated with DMD, demonstrating that no Ru-S bond cleavage is involved. Moderate diastereoselectivities are observed for the oxygen transfer to chiral, racemic thioether complexes 3 (8-28%) and 4 (34-60%). Oxidation of the (S,S)-CHIRAPHOS complexes 5, however, is highly stereoselective (de = 46-98%). Treatment of the sulfoxide complexes 10 with sodium iodide removes the chiral, nonracemic sulfoxides from the metal with retention of the configuration at sulfur.

show abstract

Section: Discussionsupporting

confidence: 43%

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹

et al. 1997

View full text Add to dashboard Cite

show abstract

“…It has been shown that in the absence of donor atoms in the ortho position, the diaryl sulfide acts as monodentate with only sulfur coordinating with the metal center [3]. In the presence of donor groups (hydroxyl, thiol, imines, amides) at the ortho position, diaryl sulfides are known to coordinate with metals such as aluminum [4], palladium [5], nickel [6], platinum [7], ruthenium [8], iron [9], lanthanide [10], germanium [11] and zinc complexes [12] in a tridentate manner, whereby the sulfur is involved in coordination or bidentate binding with no sulfur coordination. Diaryl sulfides containing dicarboxylate as a donor group have not been subjected to detailed study.…”

Section: Introductionmentioning

confidence: 99%

Versatile coordinating capabilities of thiodibenzoic acid copper complexes bearing N-donor ligands

Moosun

Blair

Coles

et al. 2014

Transition Met Chem

View full text Add to dashboard Cite

Cu(II) coordination polymers [Cu(tda)(phen)]-1.5H 2 O (1a), [Cu(tda)(py)] (2a) and [Cu(tda)(bipy)(H 2 O)]-0.5H 2 O (3a) (tda = thiodibenzoic acid, phen = phenanthroline, py = pyridine, bipy = bipyridine) have been synthesized by slow diffusion. Under solvothermal conditions, [Cu(tda)(phen)]2H 2 O (1b), [Cu(tda)(H 2 O)] (2b) and[Cu(tda)(bipy)] (3b) were isolated. The structures of the complexes 1a-3a have been determined by single X-ray diffraction. The experimental X-ray powder diffraction patterns of 1b-3b were compared with the calculated patterns of 1a-3a. The polymers were found to exhibit structural and dimensional diversity due to the effect of the co-ligands. In complexes 1a and 1b, tda is found to coordinate with the metal atom in a monodentate mode, while in 2a and 2b, the carboxylate oxygens are coordinated with the two metal centers in a l-bridged bidentate fashion. The structural analysis of 3a shows that the copper atom is in a square pyramidal environment, whereby the metal atom is coordinated with the carboxylate oxygens of two different tda ligands in a monodentate fashion and two nitrogens of the bipyridine ligand and one coordinated water. The IR spectrum of 3b implies a bidentate mode of coordination.

show abstract

“…Following specific irradiation, decay of the inversion was monitored at (/ 40 8 via the measurement of absolute peak height of all four signal. In this way the free energy of inversions were measured and found to be 499/1 kJ mol (1 ; although this is within the range found for related systems [4,13] it is significantly greater than the 30 kJ mol (1 found for [RuCp(dppe)SEt 2 ] [14].…”

Section: Resultsmentioning

confidence: 79%

Chiral ruthenium complexes with sulfur ligands; X-ray structure of (R)Ru-Ru(NmCp)(CO)(PPh3)SCN (NmCp=neomenthylcyclopentadienyl)

Tabatabaeian

Downing

Adams

et al. 2003

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Relative stability of η5-cyclopentadienyl(olefin)ruthenium cations: The first estimation of the nature of the RuII-olefin bond

Cited by 15 publications

References 19 publications

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹

Versatile coordinating capabilities of thiodibenzoic acid copper complexes bearing N-donor ligands

Chiral ruthenium complexes with sulfur ligands; X-ray structure of (R)Ru-Ru(NmCp)(CO)(PPh3)SCN (NmCp=neomenthylcyclopentadienyl)

Contact Info

Product

Resources

About

Relative stability of η5-cyclopentadienyl(olefin)ruthenium cations: The first estimation of the nature of the RuII-olefin bond

Cited by 15 publications

References 19 publications

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides1

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides1

Versatile coordinating capabilities of thiodibenzoic acid copper complexes bearing N-donor ligands

Chiral ruthenium complexes with sulfur ligands; X-ray structure of (R)Ru-Ru(NmCp)(CO)(PPh3)SCN (NmCp=neomenthylcyclopentadienyl)

Contact Info

Product

Resources

About

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides¹