CO insertion in four-coordinate cis-methyl(carbonyl)platinum-diphosphine compounds. An ionic mechanism for platinum-diphosphine-catalyzed hydroformylation

Imre Tóth, T. Kégl, Cornelis J. Elsevier, L. Kollár

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

The reactions of the square-planar methylplatinum-cis-diphosphine complexes, Pt(Me)(Cl){(S,S)-BDPP}, 1, and Pt(Me)(SnCl3){(S,S)-BDPP}, 2, (BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) with CO, and a mixture of CO/H2 = 1/1 have been studied in CD2Cl2 solutions by variable temperature high-pressure NMR spectroscopy to establish the role of Pt-SnCl3 bond in the CO insertion and hydrogenolysis steps of the Pt-diphosphine-catalyzed olefin hydroformylation reaction. At low temperatures (193-213 K), the formation of the unprecedented four-coordinate ionic cis-methyl(carbonyl)platinum-diphosphine compound, [Pt(Me)(CO){(S,S)-BDPP}]+X- where X = Cl, 3a, and X = SnCl3, 3b, has been observed whether CO is applied neat or in a mixture with hydrogen. The formation of compounds 3a and 3b involve equilibrium reactions which are facilitated by increasing the CO pressure; however, while the formation of 3b is a fast (magnitudes faster than that of 3a at identical conditions) and quantitative reaction, the formation of compound 3a remains a slow reaction that does not reach completion in the range of 1-50 bar of CO pressure. CO insertion in compounds 3a and 3b takes place only at temperatures close to ambient, yielding covalent acetyl compound Pt(COMe)(Cl){(S,S)-BDPP}, 4, and ionic acetyl compound [Pt(COMe)(CO){(S,S)-BDPP}]+SnCl3-, 5, respectively. At room temperature, 5 but not 4 reacts further in the presence of hydrogen, resulting in the formation of acetaldehyde and an unidendified Pt-diphosphine compound. Thus, it appears that the hydroformylation by Pt-BDPP complexes proceeds via an ionic reaction mechanism.

Original languageEnglish
Pages (from-to)5708-5712
Number of pages5
JournalInorganic Chemistry
Volume33
Issue number25
Publication statusPublished - 1994

Fingerprint

platinum compounds
Platinum Compounds
Hydroformylation
Platinum
insertion
platinum
acetyl compounds
Hydrogen
Temperature
Hydrogenolysis
Acetaldehyde
ionic reactions
Alkenes
hydrogenolysis
Nuclear magnetic resonance spectroscopy
acetaldehyde
pentanes
hydrogen
alkenes
nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

CO insertion in four-coordinate cis-methyl(carbonyl)platinum-diphosphine compounds. An ionic mechanism for platinum-diphosphine-catalyzed hydroformylation. / Tóth, Imre; Kégl, T.; Elsevier, Cornelis J.; Kollár, L.

In: Inorganic Chemistry, Vol. 33, No. 25, 1994, p. 5708-5712.

Research output: Contribution to journalArticle

@article{eb28798843874187acce0d32d40a584d,
title = "CO insertion in four-coordinate cis-methyl(carbonyl)platinum-diphosphine compounds. An ionic mechanism for platinum-diphosphine-catalyzed hydroformylation",
abstract = "The reactions of the square-planar methylplatinum-cis-diphosphine complexes, Pt(Me)(Cl){(S,S)-BDPP}, 1, and Pt(Me)(SnCl3){(S,S)-BDPP}, 2, (BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) with CO, and a mixture of CO/H2 = 1/1 have been studied in CD2Cl2 solutions by variable temperature high-pressure NMR spectroscopy to establish the role of Pt-SnCl3 bond in the CO insertion and hydrogenolysis steps of the Pt-diphosphine-catalyzed olefin hydroformylation reaction. At low temperatures (193-213 K), the formation of the unprecedented four-coordinate ionic cis-methyl(carbonyl)platinum-diphosphine compound, [Pt(Me)(CO){(S,S)-BDPP}]+X- where X = Cl, 3a, and X = SnCl3, 3b, has been observed whether CO is applied neat or in a mixture with hydrogen. The formation of compounds 3a and 3b involve equilibrium reactions which are facilitated by increasing the CO pressure; however, while the formation of 3b is a fast (magnitudes faster than that of 3a at identical conditions) and quantitative reaction, the formation of compound 3a remains a slow reaction that does not reach completion in the range of 1-50 bar of CO pressure. CO insertion in compounds 3a and 3b takes place only at temperatures close to ambient, yielding covalent acetyl compound Pt(COMe)(Cl){(S,S)-BDPP}, 4, and ionic acetyl compound [Pt(COMe)(CO){(S,S)-BDPP}]+SnCl3-, 5, respectively. At room temperature, 5 but not 4 reacts further in the presence of hydrogen, resulting in the formation of acetaldehyde and an unidendified Pt-diphosphine compound. Thus, it appears that the hydroformylation by Pt-BDPP complexes proceeds via an ionic reaction mechanism.",
author = "Imre T{\'o}th and T. K{\'e}gl and Elsevier, {Cornelis J.} and L. Koll{\'a}r",
year = "1994",
language = "English",
volume = "33",
pages = "5708--5712",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - CO insertion in four-coordinate cis-methyl(carbonyl)platinum-diphosphine compounds. An ionic mechanism for platinum-diphosphine-catalyzed hydroformylation

AU - Tóth, Imre

AU - Kégl, T.

AU - Elsevier, Cornelis J.

AU - Kollár, L.

PY - 1994

Y1 - 1994

N2 - The reactions of the square-planar methylplatinum-cis-diphosphine complexes, Pt(Me)(Cl){(S,S)-BDPP}, 1, and Pt(Me)(SnCl3){(S,S)-BDPP}, 2, (BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) with CO, and a mixture of CO/H2 = 1/1 have been studied in CD2Cl2 solutions by variable temperature high-pressure NMR spectroscopy to establish the role of Pt-SnCl3 bond in the CO insertion and hydrogenolysis steps of the Pt-diphosphine-catalyzed olefin hydroformylation reaction. At low temperatures (193-213 K), the formation of the unprecedented four-coordinate ionic cis-methyl(carbonyl)platinum-diphosphine compound, [Pt(Me)(CO){(S,S)-BDPP}]+X- where X = Cl, 3a, and X = SnCl3, 3b, has been observed whether CO is applied neat or in a mixture with hydrogen. The formation of compounds 3a and 3b involve equilibrium reactions which are facilitated by increasing the CO pressure; however, while the formation of 3b is a fast (magnitudes faster than that of 3a at identical conditions) and quantitative reaction, the formation of compound 3a remains a slow reaction that does not reach completion in the range of 1-50 bar of CO pressure. CO insertion in compounds 3a and 3b takes place only at temperatures close to ambient, yielding covalent acetyl compound Pt(COMe)(Cl){(S,S)-BDPP}, 4, and ionic acetyl compound [Pt(COMe)(CO){(S,S)-BDPP}]+SnCl3-, 5, respectively. At room temperature, 5 but not 4 reacts further in the presence of hydrogen, resulting in the formation of acetaldehyde and an unidendified Pt-diphosphine compound. Thus, it appears that the hydroformylation by Pt-BDPP complexes proceeds via an ionic reaction mechanism.

AB - The reactions of the square-planar methylplatinum-cis-diphosphine complexes, Pt(Me)(Cl){(S,S)-BDPP}, 1, and Pt(Me)(SnCl3){(S,S)-BDPP}, 2, (BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) with CO, and a mixture of CO/H2 = 1/1 have been studied in CD2Cl2 solutions by variable temperature high-pressure NMR spectroscopy to establish the role of Pt-SnCl3 bond in the CO insertion and hydrogenolysis steps of the Pt-diphosphine-catalyzed olefin hydroformylation reaction. At low temperatures (193-213 K), the formation of the unprecedented four-coordinate ionic cis-methyl(carbonyl)platinum-diphosphine compound, [Pt(Me)(CO){(S,S)-BDPP}]+X- where X = Cl, 3a, and X = SnCl3, 3b, has been observed whether CO is applied neat or in a mixture with hydrogen. The formation of compounds 3a and 3b involve equilibrium reactions which are facilitated by increasing the CO pressure; however, while the formation of 3b is a fast (magnitudes faster than that of 3a at identical conditions) and quantitative reaction, the formation of compound 3a remains a slow reaction that does not reach completion in the range of 1-50 bar of CO pressure. CO insertion in compounds 3a and 3b takes place only at temperatures close to ambient, yielding covalent acetyl compound Pt(COMe)(Cl){(S,S)-BDPP}, 4, and ionic acetyl compound [Pt(COMe)(CO){(S,S)-BDPP}]+SnCl3-, 5, respectively. At room temperature, 5 but not 4 reacts further in the presence of hydrogen, resulting in the formation of acetaldehyde and an unidendified Pt-diphosphine compound. Thus, it appears that the hydroformylation by Pt-BDPP complexes proceeds via an ionic reaction mechanism.

UR - http://www.scopus.com/inward/record.url?scp=33751157204&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33751157204&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:33751157204

VL - 33

SP - 5708

EP - 5712

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 25

ER -