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Isolation and characterization of the acyl complexestrans-[Pt(PPh3)2(COR)Cl] (R =nBu orsBu) and their relevance to the hydroformylation of linear butenes catalyzed by platinum/tin/triphenylphosphine catalytic systems. Molecular structure ofcis- [Pt(PPh3)2Cl(SnCl3)]
- Source :
- Journal of Organometallic Chemistry. 466:277-282
- Publication Year :
- 1994
- Publisher :
- Elsevier BV, 1994.
-
Abstract
- The acyl complex trans -[Pt(PPh 3 ) 2 (CO n Bu)Cl] ( A ) has been synthesized by reaction of [Pt(PPh 3 ) 2 Cl 2 ] with 1-butene under 100 atm of CO at 80–100°C, in ethanol. With 2-butene rather than 1-butene under the same conditions, a mixture of the above acyl complex and of trans - [Pt(PPh 3 ) 2 (CO s Bu)Cl] ( B ) was formed. Complexes A and B do not interconvert. The new acyl complexes A and B have been characterized by IR and 1 H NMR and 13 C NMR spectroscopy. The ratio A / B increases with PPh 3 /Pt ratio and with temperature. The formation of two isomers when 2-butene is used involves an isomerization process which is likely to be limited to the alkyl precursor complexes. The reactivity of complexes A and B has been tested in reactions with SnCl 2 , H 2 , HCl and trans -[Pt(PPh 3 ) 2 HCl]. From the reaction solutions crystals of cis -[Pt(PPh 3 ) 2 Cl(SnCl 3 )] have been obtained. Its molecular structure has been determined by X-ray diffraction. The Pt atom has cis square planar coordination, with angular distortions due to steric factors. The strong trans influence of the SnCl 3 group is confirmed by the lengthening of the trans Pt-P distance. The SnCl 3 group has the pyramidal geometry found in all related compounds.
- Subjects :
- Steric effects
Stereochemistry
Trans effect
Organic Chemistry
chemistry.chemical_element
Butenes
Hydroformylation
Platinum
X-ray structure
Biochemistry
Medicinal chemistry
Catalysis
Inorganic Chemistry
chemistry.chemical_compound
chemistry
Materials Chemistry
Reactivity (chemistry)
Physical and Theoretical Chemistry
Triphenylphosphine
Isomerization
Subjects
Details
- ISSN :
- 0022328X
- Volume :
- 466
- Database :
- OpenAIRE
- Journal :
- Journal of Organometallic Chemistry
- Accession number :
- edsair.doi.dedup.....e29a76f4358d97bcbcffbbebba0f8cb7