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Transformation of a Trialkynylphosphine Oxide to a 2-Alkylidene-1,2 dihydro-3-phosphete P-Oxide Ligand by Pt-H Addition and Rearrangement Reactions. Activation of Molecular Hydrogen by a Platinum(II) Complex

Publication ,  Journal Article
Lukehart, CM; McPhail, AT; McPhail, DR; Myers, JB; Soni, HK
Published in: Organometallics
January 1, 1989

Addition of the Pt—H bond of [trans-Pt(H)(PEt3)2(THF)]+ to the C≡C triple bond of the alkynyl substituent of O=PPh2(C≡CPh) occurs regioselectively to give a Pt, P μ-alkenylidene complex. Similar addition of a Pt—H bond to the trialkynylphosphine oxide O=P(C≡CCMe3)3 presumably occurs also, but a facile insertion rearrangement takes place to form a novel 2-alkylidene-1,2-dihydro-3-phosphete P-oxide ligand. Complexes containing this heterocyclic alkenyl ligand react with molecular hydrogen at -78 °C and at atmospheric pressure to give neutral monohydride complexes. The X-ray structure of one such complex has been determined: {trans-Pt[C=C(CMe3)P(OBF3)(C≡CCMe3)C==C(CMe3)(H)][P(n-Pr)3]2(H)}; monoclinic; P21/c; Z = 4;a = 11.006 (4) Å, b = 21.435 (5) Å, c = 19.518 (5) Å; β= 100.72 (3)°. Other reaction chemistry and a discussion of proposed mechanisms for the formation of these unusual complexes are reported. © 1989, American Chemical Society. All rights reserved.

Duke Scholars

Published In

Organometallics

DOI

EISSN

1520-6041

ISSN

0276-7333

Publication Date

January 1, 1989

Volume

8

Issue

4

Start / End Page

1007 / 1014

Related Subject Headings

  • Organic Chemistry
  • 3406 Physical chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0305 Organic Chemistry
  • 0302 Inorganic Chemistry
 

Citation

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Lukehart, C. M., McPhail, A. T., McPhail, D. R., Myers, J. B., & Soni, H. K. (1989). Transformation of a Trialkynylphosphine Oxide to a 2-Alkylidene-1,2 dihydro-3-phosphete P-Oxide Ligand by Pt-H Addition and Rearrangement Reactions. Activation of Molecular Hydrogen by a Platinum(II) Complex. Organometallics, 8(4), 1007–1014. https://doi.org/10.1021/om00106a022
Lukehart, C. M., A. T. McPhail, D. R. McPhail, J. B. Myers, and H. K. Soni. “Transformation of a Trialkynylphosphine Oxide to a 2-Alkylidene-1,2 dihydro-3-phosphete P-Oxide Ligand by Pt-H Addition and Rearrangement Reactions. Activation of Molecular Hydrogen by a Platinum(II) Complex.” Organometallics 8, no. 4 (January 1, 1989): 1007–14. https://doi.org/10.1021/om00106a022.
Journal cover image

Published In

Organometallics

DOI

EISSN

1520-6041

ISSN

0276-7333

Publication Date

January 1, 1989

Volume

8

Issue

4

Start / End Page

1007 / 1014

Related Subject Headings

  • Organic Chemistry
  • 3406 Physical chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0305 Organic Chemistry
  • 0302 Inorganic Chemistry