Macrocyclic titanium thiolate metalloligands: complexation and thiolate-transfer reactions with copper(I), nickel(II), palladium(II)

Huang, Yujin; Drake, Robert J.; Stephan, Douglas W.

doi:10.1021/ic00066a011

Cited by 45 publications

(14 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Ligand redistribution reactions are thought to occur via a dimeric intermediate in which bridging thiolate ligands are exchanged between the two metal centers (Scheme ). The notion of a dimeric intermediate is conceptually supported by the structural data for the related trithiolate compound [Cp*Zr(SR) 2 (μ-SR)] 2 as well as the thiolate-bridged titanium compound [CpTi(μ 2 -SCH 2 CH 2 S)Cl] 2 . While these species are dynamic in solution, their dimeric nature in the solid state has been confirmed.…”

Section: Resultsmentioning

confidence: 86%

Thermal Reactions of Titanium Thiolates: Terminal Titanium Sulfides in CS Bond Cleavage Reactions

1998

Self Cite

View full text Add to dashboard Cite

The thermolysis of monocyclopentadienyltitanium thiolate complexes leads to ligand redistributions and C-S bond cleavage reactions. Kinetic study of the C-S bond thermolysis reaction of CpTi(OC 6 H 3 -2,6-i-Pr 2 )(SBn) 2 (2) to the sulfide-bridged dimer [CpTi(OC 6 H 3 -2,6i-Pr 2 )(µ-S)] 2 (1) is shown to be first order in 2, consistent with an intramolecular process proceeding via a terminal sulfide intermediate and rapid dimerization (k ) 2.8 × 10 -6 s -1 ). The related species CpTi(OC 6 H 3 -2,6-i-Pr 2 )(SBn)Cl (3), CpTi(OC 6 H 3 -2,6-i-Pr 2 )(SMe) 2 (4), and CpTi(OC 6 H 3 -2,6-i-Pr 2 )(SPh) 2 (5) are thermally stable, although compounds 4 and 5 undergo thermally induced ligand redistribution reactions. These redistribution reactions are thought to occur via a dimeric intermediate in which bridging thiolate ligands are exchanged between two metal centers. A dimeric intermediate is supported by the characterization of the species [CpTi(SR) 2 (µ-SR)] 2 (R ) Et (7), Bn (8)) which are dimeric in solution at low temperature and in the solid state. In contrast, Cp*Ti(SBn) 3 ( 9) is monomeric. Efforts to intercept a terminal sulfide intermediate in the formation of 1 were unsuccessful, although reaction of CpTiCl 2 Me with LiSBn in the presence of PMe 3 gives [CpTiCl(µ-S)] 2 [PMe 3 Bn] (10) in low yield. The analogue of 2, Cp*Ti(OC 6 H 3 -2,6-i-Pr 2 )(SBn) 2 , 12, is thermally stable; however, thermolysis of Cp*TiCl(SBn) 2 gave [Cp*TiCl(µ-S)] 2 (13). Ultimately, the LiCl adduct of a terminal sulfide species Cp*Ti(OC 6 H 3 -2,6-i-Pr 2 )(µ-S)(µ-Cl)Li(THF) 2 ( 14) was isolated from the reaction of Cp*Ti(OC 6 H 3 -2,6-i-Pr 2 )Cl 2 (11) with Li 2 S. Treatment of ( 14) with PMe 3 generates the monomeric terminal sulfide complex species Cp*Ti(OC 6 H 3 -2,6-i-Pr 2 )(S)(PMe 3 ) (15), which is unstable, slowly evolving PMe 3 affording [Cp*Ti(OC 6 H 3 -2,6-i-Pr 2 )(µ-S)] 2 (16). Compound 16 is also obtained directly by heating solutions of 14. Crystallographic studies of 8, 10, 12, 13, 14, and 16 are reported herein. The intermediacy of terminal metal sulfides in C-S processes are discussed. species by sulfur. C-S bond cleavage is an alternative route to M-S bond formation. The research groups of Winter 12 and Bochmann 13 have produced TiS and TiS 2 films from titanium thiolate precursors. In an analogous manner, M-S aggregates as Zr 3 S 3 (t-BuS) 2 (BH 4 ) 4 -(THF) 2 and Zr 6 S 6 (t-BuS) 4 (BH 4 ) 8 (THF) 2 , 14 Zr 3 S(S-t-Bu) 10 , 15 (CpTi) 4 (µ 3 -S) 3 (µ 2 -S)(µ 2 -SEt) 2 , (CpTi) 6 (µ 3 -S) 4 (µ 3 -O) 4 , 16 and [(CpTi(OC 6 H 3 -2,6-i-Pr 2 )(µ 3 -S)] 3 TiCp 17 have been prepared via C-S bond thermolysis reactions. Some of the more recent examples are depicted in Scheme 1. More recently, we have described the high-yield thermolysis of CpTi(OC 6 H 3 -2,6-i-Pr 2 )(SBn) 2 (2) to the sulfide-bridged dimer [CpTi(OC 6 H 3 -2,6-i-Pr 2 )(µ-S)] 2 (1). 17 Unlike the complex reactions affording larger M-S aggregates, the reactions of discrete monocyclopentadienyltitanium thiolate complexes, a class of compounds that has drawn little ...

show abstract

Section: Resultsmentioning

confidence: 86%

Thermal Reactions of Titanium Thiolates: Terminal Titanium Sulfides in CS Bond Cleavage Reactions

1998

Self Cite

View full text Add to dashboard Cite

show abstract

“…The formation of early−late heterobimetallic complexes always competes with the ligand transfer of the potential bridging ligands to the d 8 metal centers. This is particulary frequent in the case of thiolato ligands, so that some thiolate ligand transfer reactions from thiolatotitanocene or thiolatozirconocene complexes have been recently used to prepare the corresponding thiolato complexes of the late transition metals Co, Rh, Pd, and Pt . These ligand transfer reactions are believed to proceed through an associative pathway involving a heterobimetallic intermediate where the ligand redistribution takes place 31b…”

Section: Discussionmentioning

confidence: 99%

Deprotonation of Cp₂Ti(SH)₂ with Mononuclear Rhodium and Iridium Compounds: A New Route to Trinuclear Early−Late Heterobimetallic Complexes

et al. 1999

View full text Add to dashboard Cite

The reaction of Cp 2 Ti(SH) 2 with [M(acac)(diolefin)] (acac ) acetylacetonate) yields the complexes [Cp(acac)Ti(µ 3 -S) 2 {M(diolefin)} 2 ] (M ) Rh, diolefin ) 1,5-cyclooctadiene (cod) (1); diolefin ) tetrafluorobenzobarrelene (tfbb) (2); M ) Ir, diolefin ) cod ( 3)). The formation of the trinuclear heterobimetallic complexes results from a complex reaction involving the deprotonation of the hydrosulfido ligands along with the addition of the late-metal fragment-(s), followed by the release of cyclopentadiene and the coordination of acetylacetonate to the titanium center. Similarly, the reaction of Cp 2 Ti(SH) 2 with [M(quinol)(diolefin)] (quinol ) 8-oxyquinolinate) gives the complexes [Cp(quinol)Ti(µ 3 -S) 2 {M(diolefin)} 2 ] (M ) Rh, diolefin ) cod (4); tfbb (5); M ) Ir, diolefin ) cod ( 6)), which incorporate the 8-oxyquinolinate ligand. The d 0 -d 8 trinuclear early-late heterobimetallic complexes exhibit triangular TiRh 2 and TiIr 2 cores doubly capped by two µ 3 -sulfido ligands. Deprotonation of Cp 2 Ti(SH) 2 with the mononuclear carbonyl complexes [M(acac)(CO) 2 ] (M ) Rh, Ir) yields the ion-pair complexes [Cp 2 Ti(acac)][M 3 (µ 3 -S) 2 (CO) 6 ] (M ) Rh ( 7); M ) Ir ( 8)), which result from complete transference of the sulfido ligands to the d 8 metal centers. Carbonylation of the diolefin complexes 9); M ) Ir ( 10)) and [Cp(quinol)Ti(µ 3 -S) 2 {M(CO) 2 } 2 ] (M ) Rh (11); M ) Ir ( 12)), respectively. Replacement reactions on the carbonyl complexes with triphenylphosphine give the disubstituted complexes [Cp(acac)Ti(µ 3 -S) 2 -{M(CO)(PPh 3 )} 2 ] (M ) Rh (13); M ) Ir ( 14)) or [Cp(quinol)Ti(µ 3 -S) 2 {M(CO)(PPh 3 )} 2 ] (M ) Rh (15); M ) Ir ( 16)), which are obtained as mixtures of cis and trans isomers. The molecular structures of complexes 1 and 8 have been determined by X-ray diffraction methods.

show abstract

“…B. [15,16,17]. Zwischen dem Palladium-Atom und den Thioetherschwefel-Atomen sind jedoch keine bindenden Wechselwirkungen nachweisbar, die Palladium±Thioetherschwefel-Absta È nde betragen 3,11 und 3,93 A Ê .…”

Section: Introductionunclassified

Synthese, Struktur und Charakterisierung von Titan-, Zink-, Nickel- und Palladium-Thioether-Thiolat-Komplexen heterocyclischer 1,2-Dithiolate

Zeltner

Olk

Jörchel

et al. 1999

Z. anorg. allg. Chem.

View full text Add to dashboard Cite

Synthese und Eigenschaften von Gemischtligandenkomplexen der Thioether‐Thiolat‐Liganden 4‐Methylthio‐1,3‐dithiol‐2‐on‐5‐thiolat (dmidCH3), 4‐Methylthio‐1,3‐dithiol‐2‐thion‐5‐thiolat (dmitCH3) und 4‐Methylthio‐1,3‐dithiol‐2‐selon‐5‐thiolat (dmiseCH3) werden beschrieben. Die Röntgenkristallstrukturanalysen von Cp ′2Ti(dmidCH3)2 (Cp′ = Methylcyclopentadienyl), von zwei polymorphen Modifikationen des (tmeda)Zn(dmitCH3)2 [tmeda = 1,2‐Bis(dimethylamino)ethan] sowie von (dppe)Ni(dmitCH3)2 und (dppe)Pd(dmitCH3)2 [dppe = 1,2‐Bis(diphenylphosphino)ethan] werden vorgestellt.

show abstract

Macrocyclic titanium thiolate metalloligands: complexation and thiolate-transfer reactions with copper(I), nickel(II), palladium(II)

Cited by 45 publications

References 0 publications

Thermal Reactions of Titanium Thiolates: Terminal Titanium Sulfides in CS Bond Cleavage Reactions

Thermal Reactions of Titanium Thiolates: Terminal Titanium Sulfides in CS Bond Cleavage Reactions

Deprotonation of Cp₂Ti(SH)₂ with Mononuclear Rhodium and Iridium Compounds: A New Route to Trinuclear Early−Late Heterobimetallic Complexes

Synthese, Struktur und Charakterisierung von Titan-, Zink-, Nickel- und Palladium-Thioether-Thiolat-Komplexen heterocyclischer 1,2-Dithiolate

Contact Info

Product

Resources

About

Macrocyclic titanium thiolate metalloligands: complexation and thiolate-transfer reactions with copper(I), nickel(II), palladium(II)

Cited by 45 publications

References 0 publications

Thermal Reactions of Titanium Thiolates: Terminal Titanium Sulfides in CS Bond Cleavage Reactions

Thermal Reactions of Titanium Thiolates: Terminal Titanium Sulfides in CS Bond Cleavage Reactions

Deprotonation of Cp2Ti(SH)2 with Mononuclear Rhodium and Iridium Compounds: A New Route to Trinuclear Early−Late Heterobimetallic Complexes

Synthese, Struktur und Charakterisierung von Titan-, Zink-, Nickel- und Palladium-Thioether-Thiolat-Komplexen heterocyclischer 1,2-Dithiolate

Contact Info

Product

Resources

About

Deprotonation of Cp₂Ti(SH)₂ with Mononuclear Rhodium and Iridium Compounds: A New Route to Trinuclear Early−Late Heterobimetallic Complexes