211870-85-8

Upstream product

• 273217-80-4 cis-Pt(PMe₂Ph)2(SiPh₃)CH₂CD₃ 
• 501-65-5 diphenyl acetylene 
• 182009-40-1 cis-Pt(PMe₂Ph)2(SiPh₃)Et 
• 173396-10-6 cis-PtMe(SiPh₃)(PMe₂Ph)2 
• 12112-64-0 trans-chlorobis(dimethylphenylphosphine)hydridoplatinum(II) 

Relevant academic research and scientific papers

Kinetic studies on the reductive elimination of cis-PtMe(SiPh3)(PMe2Ph)2 and cis-PtMe(GePh3)(PMe2Ph)2. The first comparison between C-Si and C-Ge reductive elimination

The novel complex cis-PtMe(GePh3)(PMe2Ph)2 (2b) was prepared by the treatment of trans-PtCl(GePh3)(PMe2Ph)2 (3) with 2 equiv of MeLi in THF followed by methanolysis of the reaction system.

Platinum-catalyzed bis-germylation of alkynes with organodigermanes and cyclic oligogermanes

Hexamethyldigermane, Me3GeGeMe3, reacted with various alkynes in the presence of platinum complexes at 120 °C to afford Z-1,2-bis(germyl)ethenes in moderate to good yields. Terminal alkynes exhibit higher reactivities than internal ones. [Pt(acac)2] and [Pt(dba)2] serve as efficient catalysts, while [Pt(PPh3)4], [PtCl2(PPh3)2], and [Pt(dba)2]-phosphite were found to be inactive. Four- and six-membered cyclic oligogermanes, such as dodecamethylcyclohexagermane, (Me2Ge)6, reacted with alkynes in the presence of platinum catalysts to yield 1,4-digermacyclohexa-2,5-dienes in ca. 30% yield. The reactions of phenylacetylene with 1,2-digermacyclohexa-3,5-dienes afforded the corresponding 1,4-digermacycloocta-2,5,7-trienes in 93% yield. Bis(germyl)platinum complexes having various tertiary phosphine ligands have been prepared as models of a key intermediate in the above mentioned catalytic bis-germylation of alkynes, and their structures have been established by spectroscopic methods and X-ray crystallography. Bis(germyl)platinum complexes reacted with phenylacetylene to give the corresponding insertion products, germyl(germylvinyl)platinum species, whose structures have been determined by spectroscopic and X-ray analysis. Germyl(germylvinyl)platinum complexes were found to liberate a bis-germylation product of the alkyne upon heating. The result supports a mechanism involving the oxidative addition of a digermane to a Pt(0) complex, the insertion of an alkyne into one of the two Pt-Ge bonds to give a germyl(germylvinyl)platinum species, and the reductive elimination of the bis-germylation product of the alkyne. Evidence suggesting the extrusion of a germylene unit from the bis-germylplatinum species has been obtained, accounting for the generation courses of other by-products.

Thermolysis reactions of cis-PtR(SiPh3)(PMe2Ph)2 in solution

A series of trans- and cis-PtR(SiPh3)(PMe2Ph)2 complexes have been prepared and their thermolysis reactions in solution examined. The trans isomers (R = Me, Et) are robust, and only the methyl complex affords MeSiPh3 as the reductive elimination product in 72-82% yields. In contrast, the cis isomers (R = Me, Et, Pr, Bu) form the corresponding alkylsilanes in almost quantitative yields (>97%). Despite the selective formation of the reductive elimination products, the cis-alkyl-silyl complexes bearing β-hydrogens undergo a rapid repetition of the β-hydrogen elimination and insertion processes, as confirmed by a deuterium-labeling experiment using cis-Pt(CH2CD3)(SiPh3)(PMe2Ph) 2. The alkylsilane formation from the cis isomers proceeds via two reaction paths. One is the direct C-Si reductive elimination. On the other path, the cis-PtR(SiPh3)(PMe2Ph)2 complexes are initially isomerized to the corresponding cis-PtPh(SiRPh2)(PMe2Ph)2 complexes by the exchange of the Pt-R group with the Si-Ph group, and the resulting phenyl-silyl complexes reductively eliminate alkylsilanes. The methyl-silyl complex decomposes exclusively by the former path, while the other alkyl-silyl complexes (R = Et, Pr, Bu) follow mainly the latter path. Preparation and thermolysis reaction of the related cis-PtEt(GePh3)(PMe2Ph)2 are also reported.