Transformation of the Bis(diphenylphosphino)methane Ligand on the Ru3(CO)9Framework. Synthesis and Characterization of Ru3(CO)933-P(C6H5)CH2P(C6H5)(C6H4)), Ru3(CO)9(μ-H)(μ32-P(C6H5)CH2P(C6H5)2), and Ru3(CO)10(μ-η2-P(C6H5)CH2P(C6H5)(C6H4))

Noël Lugan, Jean Jacques Bonnet, James A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticle

113 Scopus citations

Abstract

Several transformations of the dppm ligand on Ru3 clusters have been established (dppm = bis(diphenylphosphino)methane), starting from the parent complex Ru3(c6)10(μ-η2-dppm), 1. In compound 2, Ru3(Co)9(μ3-η3-P-(C6H5)CH2P(C6H5)(C6H4)), the Ru3(CO)9 fragment is bridged by the six-electron tridentate phosphine ligand. In compound 3, Ru3(Co)9(μ-H)(μ32-P(C6H5)CH2P(C6H5)2), the Ru3(CO)9H fragment is bridged in a bidentate manner by the five-electron phosphine donor. In compound 4, Ru3(Co)10(μ-η2-P(C6H5)Ch2P(C6H5)(C6H4)), the Ru3(CO)l0 fragment is bridged in a bidentate manner by the four-electron phosphine ligand. Thermolysis of 1 at 80 °C in cyclohexane affords 2 in high yield. Thermolysis of 2 in the presence of H2 affords 3 in high yield. Compound 3 can also be produced directly from 1 at 90 °C in toluene. When CO is bubbled through a solution of 2 in refluxing cyclohexane, compound 4 is produced in high yield. Compound 4 reacts with H2 under reflux in cyclohexane to yield compound 3. When compound 4 is refluxed in cyclohexane under N2, compound 2 results. The nature of compounds 2, 3, and 4 has been established by spectroscopic means and by X-ray diffraction methods: crystal data, 2, monoclinic, C2h5-P21/c, Z = 4,a = 10.689 (7) Å, b = 11.936 (7) Å, c = 23.281 (18) Å, β = 90.18 (8)° (t = -85 °C), final RiF2) = 3.8%, NO = 7725, NV = 381; 3, monoclinic, C2hs-P2l/n, Z = 4, a = 10.593 (2) Å, b = 13.850 (2) Å, c = 20.720 (3) Å, β= 94.12 (1)° (t = -155 °C), final R(F2) = 3.5%, NO = 7037, NV = 384; 4, monoclinic, C2h5-P21/n, Z = 4, a = 12.022 (1) A, b = 15.266 (1) A, c = 17.225 (2) A, β= 105.56 (1)° (t = -155 °C), final R(F2) = 3.5%, NO = 6755, NV = 400.

Original languageEnglish (US)
Pages (from-to)4484-4491
Number of pages8
JournalJournal of the American Chemical Society
Volume107
Issue number15
DOIs
StatePublished - Jul 1985

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Transformation of the Bis(diphenylphosphino)methane Ligand on the Ru<sub>3</sub>(CO)<sub>9</sub>Framework. Synthesis and Characterization of Ru<sub>3</sub>(CO)<sub>9</sub>(μ<sub>3</sub>-η<sup>3</sup>-P(C<sub>6</sub>H<sub>5</sub>)CH<sub>2</sub>P(C<sub>6</sub>H<sub>5</sub>)(C<sub>6</sub>H<sub>4</sub>)), Ru<sub>3</sub>(CO)<sub>9</sub>(μ-H)(μ<sub>3</sub>-η<sup>2</sup>-P(C<sub>6</sub>H<sub>5</sub>)CH<sub>2</sub>P(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>), and Ru<sub>3</sub>(CO)<sub>10</sub>(μ-η<sup>2</sup>-P(C<sub>6</sub>H<sub>5</sub>)CH<sub>2</sub>P(C<sub>6</sub>H<sub>5</sub>)(C<sub>6</sub>H<sub>4</sub>))'. Together they form a unique fingerprint.

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