Coordination chemistry and hydroformylation activity of platinum complexes containing 1-aryl-phospholes

Zsolt Csók, G. Keglevich, György Petöcz, L. Kollár

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

The reaction of the sterically crowded 1-aryl-phospholes (1-(2′,4′,6′-tri-isopropylphenyl)-3-methylphosphole (1), 1-(2′,4′,6′-tri-tert-butylphenyl)-3-methyl-phosphole (2) and 1-(2′,4′-di-tert-butyl-6′-methylphenyl)-3-methylphosphole (3)) with PtCl2(PhCN)2 was investigated by NMR spectroscopy. Significant differences in their reactivity towards PtCl2(PhCN)2 have been observed. Both cis-PtCl2(phosphole)(PhCN) and trans-PtCl2(phosphole)2 complexes were formed under normal reaction conditions. The corresponding reaction with the more basic 1-phenyl-3,4-dimethyl-phosphole (4) resulted in the immediate formation of cis-PtCl2(4)2 as the major product accompanied by ≈ 3% trans-PtCl2(4)2. The structure of the two types of platinum complexes in solution has been confirmed by 1J(195Pt,31P) coupling constants in 31P-NMR and several shielding effects in 1H-NMR spectrometry. The reduced aromatic character of the coordinated phosphole ligands has been confirmed by the pyramidalization of the phosphorus and the loss of the perpendicular arrangement of the phosphole and aryl rings. While the reaction of the sterically congested phospholes (1, 2) with [Rh(nbd)Cl]2 resulted in the formation of Rh(nbd)(phosphole)Cl complexes, the most basic 4 brought about the [Rh(nbd)(4)2]+ cation. Both the conversion and the regioselectivity of platinum- and rhodium-catalysed hydroformylation of styrene show strong dependence on the basicity of the phosphole ligand.

Original languageEnglish
Pages (from-to)79-84
Number of pages6
JournalJournal of Organometallic Chemistry
Volume586
Issue number1
Publication statusPublished - Jul 31 1999

Fingerprint

Hydroformylation
Platinum
platinum
Ligands
Nuclear magnetic resonance
chemistry
Regioselectivity
Rhodium
Styrene
Alkalinity
Shielding
Phosphorus
Spectrometry
nuclear magnetic resonance
Nuclear magnetic resonance spectroscopy
Cations
Spectrum Analysis
Magnetic Resonance Spectroscopy
Positive ions
ligands

Keywords

  • Hydroformylation
  • NMR
  • Phosphole
  • Platinum
  • Steric congestion

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Coordination chemistry and hydroformylation activity of platinum complexes containing 1-aryl-phospholes. / Csók, Zsolt; Keglevich, G.; Petöcz, György; Kollár, L.

In: Journal of Organometallic Chemistry, Vol. 586, No. 1, 31.07.1999, p. 79-84.

Research output: Contribution to journalArticle

@article{a89437a1570345a39caa4eef9183b774,
title = "Coordination chemistry and hydroformylation activity of platinum complexes containing 1-aryl-phospholes",
abstract = "The reaction of the sterically crowded 1-aryl-phospholes (1-(2′,4′,6′-tri-isopropylphenyl)-3-methylphosphole (1), 1-(2′,4′,6′-tri-tert-butylphenyl)-3-methyl-phosphole (2) and 1-(2′,4′-di-tert-butyl-6′-methylphenyl)-3-methylphosphole (3)) with PtCl2(PhCN)2 was investigated by NMR spectroscopy. Significant differences in their reactivity towards PtCl2(PhCN)2 have been observed. Both cis-PtCl2(phosphole)(PhCN) and trans-PtCl2(phosphole)2 complexes were formed under normal reaction conditions. The corresponding reaction with the more basic 1-phenyl-3,4-dimethyl-phosphole (4) resulted in the immediate formation of cis-PtCl2(4)2 as the major product accompanied by ≈ 3{\%} trans-PtCl2(4)2. The structure of the two types of platinum complexes in solution has been confirmed by 1J(195Pt,31P) coupling constants in 31P-NMR and several shielding effects in 1H-NMR spectrometry. The reduced aromatic character of the coordinated phosphole ligands has been confirmed by the pyramidalization of the phosphorus and the loss of the perpendicular arrangement of the phosphole and aryl rings. While the reaction of the sterically congested phospholes (1, 2) with [Rh(nbd)Cl]2 resulted in the formation of Rh(nbd)(phosphole)Cl complexes, the most basic 4 brought about the [Rh(nbd)(4)2]+ cation. Both the conversion and the regioselectivity of platinum- and rhodium-catalysed hydroformylation of styrene show strong dependence on the basicity of the phosphole ligand.",
keywords = "Hydroformylation, NMR, Phosphole, Platinum, Steric congestion",
author = "Zsolt Cs{\'o}k and G. Keglevich and Gy{\"o}rgy Pet{\"o}cz and L. Koll{\'a}r",
year = "1999",
month = "7",
day = "31",
language = "English",
volume = "586",
pages = "79--84",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "1",

}

TY - JOUR

T1 - Coordination chemistry and hydroformylation activity of platinum complexes containing 1-aryl-phospholes

AU - Csók, Zsolt

AU - Keglevich, G.

AU - Petöcz, György

AU - Kollár, L.

PY - 1999/7/31

Y1 - 1999/7/31

N2 - The reaction of the sterically crowded 1-aryl-phospholes (1-(2′,4′,6′-tri-isopropylphenyl)-3-methylphosphole (1), 1-(2′,4′,6′-tri-tert-butylphenyl)-3-methyl-phosphole (2) and 1-(2′,4′-di-tert-butyl-6′-methylphenyl)-3-methylphosphole (3)) with PtCl2(PhCN)2 was investigated by NMR spectroscopy. Significant differences in their reactivity towards PtCl2(PhCN)2 have been observed. Both cis-PtCl2(phosphole)(PhCN) and trans-PtCl2(phosphole)2 complexes were formed under normal reaction conditions. The corresponding reaction with the more basic 1-phenyl-3,4-dimethyl-phosphole (4) resulted in the immediate formation of cis-PtCl2(4)2 as the major product accompanied by ≈ 3% trans-PtCl2(4)2. The structure of the two types of platinum complexes in solution has been confirmed by 1J(195Pt,31P) coupling constants in 31P-NMR and several shielding effects in 1H-NMR spectrometry. The reduced aromatic character of the coordinated phosphole ligands has been confirmed by the pyramidalization of the phosphorus and the loss of the perpendicular arrangement of the phosphole and aryl rings. While the reaction of the sterically congested phospholes (1, 2) with [Rh(nbd)Cl]2 resulted in the formation of Rh(nbd)(phosphole)Cl complexes, the most basic 4 brought about the [Rh(nbd)(4)2]+ cation. Both the conversion and the regioselectivity of platinum- and rhodium-catalysed hydroformylation of styrene show strong dependence on the basicity of the phosphole ligand.

AB - The reaction of the sterically crowded 1-aryl-phospholes (1-(2′,4′,6′-tri-isopropylphenyl)-3-methylphosphole (1), 1-(2′,4′,6′-tri-tert-butylphenyl)-3-methyl-phosphole (2) and 1-(2′,4′-di-tert-butyl-6′-methylphenyl)-3-methylphosphole (3)) with PtCl2(PhCN)2 was investigated by NMR spectroscopy. Significant differences in their reactivity towards PtCl2(PhCN)2 have been observed. Both cis-PtCl2(phosphole)(PhCN) and trans-PtCl2(phosphole)2 complexes were formed under normal reaction conditions. The corresponding reaction with the more basic 1-phenyl-3,4-dimethyl-phosphole (4) resulted in the immediate formation of cis-PtCl2(4)2 as the major product accompanied by ≈ 3% trans-PtCl2(4)2. The structure of the two types of platinum complexes in solution has been confirmed by 1J(195Pt,31P) coupling constants in 31P-NMR and several shielding effects in 1H-NMR spectrometry. The reduced aromatic character of the coordinated phosphole ligands has been confirmed by the pyramidalization of the phosphorus and the loss of the perpendicular arrangement of the phosphole and aryl rings. While the reaction of the sterically congested phospholes (1, 2) with [Rh(nbd)Cl]2 resulted in the formation of Rh(nbd)(phosphole)Cl complexes, the most basic 4 brought about the [Rh(nbd)(4)2]+ cation. Both the conversion and the regioselectivity of platinum- and rhodium-catalysed hydroformylation of styrene show strong dependence on the basicity of the phosphole ligand.

KW - Hydroformylation

KW - NMR

KW - Phosphole

KW - Platinum

KW - Steric congestion

UR - http://www.scopus.com/inward/record.url?scp=0346549740&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0346549740&partnerID=8YFLogxK

M3 - Article

VL - 586

SP - 79

EP - 84

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1

ER -