Consecutive cyclometalation by platinum(II)

Milko van der Boom, Shyh Yeon Liou, Linda J W Shimon, Yehoshoa Ben-David, David Milstein

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The mechanism of the selective formation of the new benzylic mono- and bicyclometalated platinum(II) complexes 2a,b and 3b has been studied. Monitoring the initial sp3 C-H activation of the ligand DIPPIDH (α2-(diisopropylphosphino)isodurene; 1) and (1,5-cyclooctadiene)dimethylplatinum(II) ((COD)PtMe2) at room temperature by 31P{1H} NMR reveals that, after displacement of 1,5-cyclooctadiene, the complex cis-(DIPPIDH)(DIPPID)-PtMe (2a) is formed selectively by oxidative addition of a benzylic C-H bond and subsequent reductive elimination of CH4. This reaction is controlled by electronic factors. Heating of 2a results in isomerization to the thermodynamically more stable isomer trans-(DIPPIDH)-(DIPPID)PtMe (2b) as well as the formation of the double-C-H activated complex trans-(DIPPID)2Pt (3b) with liberation of CH4 in parallel pathways. Continuous heating results in the quantitative formation of the thermally stable 3b. Mechanistically, the second C-H activation proceeds analogously to the first one. The molecular structure of 3b, possessing two six-membered metallacycles, two methylene bridges, and two phosphines in mutually trans positions, was determined by complete single-crystal diffraction studies.

Original languageEnglish
Pages (from-to)2562-2568
Number of pages7
JournalOrganometallics
Volume15
Issue number10
Publication statusPublished - May 14 1996

Fingerprint

Platinum
platinum
Chemical activation
Phosphines
Heating
Isomerization
activation
Isomers
Molecular structure
heating
crack opening displacement
Diffraction
Nuclear magnetic resonance
Single crystals
Ligands
methylene
phosphines
isomerization
Monitoring
elimination

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

van der Boom, M., Liou, S. Y., Shimon, L. J. W., Ben-David, Y., & Milstein, D. (1996). Consecutive cyclometalation by platinum(II). Organometallics, 15(10), 2562-2568.

Consecutive cyclometalation by platinum(II). / van der Boom, Milko; Liou, Shyh Yeon; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David.

In: Organometallics, Vol. 15, No. 10, 14.05.1996, p. 2562-2568.

Research output: Contribution to journalArticle

van der Boom, M, Liou, SY, Shimon, LJW, Ben-David, Y & Milstein, D 1996, 'Consecutive cyclometalation by platinum(II)', Organometallics, vol. 15, no. 10, pp. 2562-2568.
van der Boom M, Liou SY, Shimon LJW, Ben-David Y, Milstein D. Consecutive cyclometalation by platinum(II). Organometallics. 1996 May 14;15(10):2562-2568.
van der Boom, Milko ; Liou, Shyh Yeon ; Shimon, Linda J W ; Ben-David, Yehoshoa ; Milstein, David. / Consecutive cyclometalation by platinum(II). In: Organometallics. 1996 ; Vol. 15, No. 10. pp. 2562-2568.
@article{f8384faa8edd45c29cc9a6a49a4fbf4a,
title = "Consecutive cyclometalation by platinum(II)",
abstract = "The mechanism of the selective formation of the new benzylic mono- and bicyclometalated platinum(II) complexes 2a,b and 3b has been studied. Monitoring the initial sp3 C-H activation of the ligand DIPPIDH (α2-(diisopropylphosphino)isodurene; 1) and (1,5-cyclooctadiene)dimethylplatinum(II) ((COD)PtMe2) at room temperature by 31P{1H} NMR reveals that, after displacement of 1,5-cyclooctadiene, the complex cis-(DIPPIDH)(DIPPID)-PtMe (2a) is formed selectively by oxidative addition of a benzylic C-H bond and subsequent reductive elimination of CH4. This reaction is controlled by electronic factors. Heating of 2a results in isomerization to the thermodynamically more stable isomer trans-(DIPPIDH)-(DIPPID)PtMe (2b) as well as the formation of the double-C-H activated complex trans-(DIPPID)2Pt (3b) with liberation of CH4 in parallel pathways. Continuous heating results in the quantitative formation of the thermally stable 3b. Mechanistically, the second C-H activation proceeds analogously to the first one. The molecular structure of 3b, possessing two six-membered metallacycles, two methylene bridges, and two phosphines in mutually trans positions, was determined by complete single-crystal diffraction studies.",
author = "{van der Boom}, Milko and Liou, {Shyh Yeon} and Shimon, {Linda J W} and Yehoshoa Ben-David and David Milstein",
year = "1996",
month = "5",
day = "14",
language = "English",
volume = "15",
pages = "2562--2568",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Consecutive cyclometalation by platinum(II)

AU - van der Boom, Milko

AU - Liou, Shyh Yeon

AU - Shimon, Linda J W

AU - Ben-David, Yehoshoa

AU - Milstein, David

PY - 1996/5/14

Y1 - 1996/5/14

N2 - The mechanism of the selective formation of the new benzylic mono- and bicyclometalated platinum(II) complexes 2a,b and 3b has been studied. Monitoring the initial sp3 C-H activation of the ligand DIPPIDH (α2-(diisopropylphosphino)isodurene; 1) and (1,5-cyclooctadiene)dimethylplatinum(II) ((COD)PtMe2) at room temperature by 31P{1H} NMR reveals that, after displacement of 1,5-cyclooctadiene, the complex cis-(DIPPIDH)(DIPPID)-PtMe (2a) is formed selectively by oxidative addition of a benzylic C-H bond and subsequent reductive elimination of CH4. This reaction is controlled by electronic factors. Heating of 2a results in isomerization to the thermodynamically more stable isomer trans-(DIPPIDH)-(DIPPID)PtMe (2b) as well as the formation of the double-C-H activated complex trans-(DIPPID)2Pt (3b) with liberation of CH4 in parallel pathways. Continuous heating results in the quantitative formation of the thermally stable 3b. Mechanistically, the second C-H activation proceeds analogously to the first one. The molecular structure of 3b, possessing two six-membered metallacycles, two methylene bridges, and two phosphines in mutually trans positions, was determined by complete single-crystal diffraction studies.

AB - The mechanism of the selective formation of the new benzylic mono- and bicyclometalated platinum(II) complexes 2a,b and 3b has been studied. Monitoring the initial sp3 C-H activation of the ligand DIPPIDH (α2-(diisopropylphosphino)isodurene; 1) and (1,5-cyclooctadiene)dimethylplatinum(II) ((COD)PtMe2) at room temperature by 31P{1H} NMR reveals that, after displacement of 1,5-cyclooctadiene, the complex cis-(DIPPIDH)(DIPPID)-PtMe (2a) is formed selectively by oxidative addition of a benzylic C-H bond and subsequent reductive elimination of CH4. This reaction is controlled by electronic factors. Heating of 2a results in isomerization to the thermodynamically more stable isomer trans-(DIPPIDH)-(DIPPID)PtMe (2b) as well as the formation of the double-C-H activated complex trans-(DIPPID)2Pt (3b) with liberation of CH4 in parallel pathways. Continuous heating results in the quantitative formation of the thermally stable 3b. Mechanistically, the second C-H activation proceeds analogously to the first one. The molecular structure of 3b, possessing two six-membered metallacycles, two methylene bridges, and two phosphines in mutually trans positions, was determined by complete single-crystal diffraction studies.

UR - http://www.scopus.com/inward/record.url?scp=0000655540&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000655540&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000655540

VL - 15

SP - 2562

EP - 2568

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -