Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources 
of “Ru═PR2”

Hoyle, Marc-André M.; Pantazis, Dimitrios A.; Burton, Hannah M.; McDonald, Robert; Rosenberg, Lisa

doi:10.1021/om200822e

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources of “Ru═PR₂”

MPS-Authors

/persons/resource/persons216826

Pantazis, Dimitrios A.
Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

Hoyle, M.-A.-M., Pantazis, D. A., Burton, H. M., McDonald, R., & Rosenberg, L. (2011). Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources of “Ru═PR₂”. Organometallics, 30(23), 6458-6465. doi:10.1021/om200822e.

Cite as: https://hdl.handle.net/21.11116/0000-0007-4619-F

Abstract

Dehydrohalogenation of secondary diarylphosphine ruthenium complexes in the presence of benzonitrile yields stable, isolable nitrile adducts of the formula [Ru(η⁵-indenyl)(PAr₂)(NCPh)(PPh₃)], in which the terminal phosphido ligand is pyramidal at P and contains a stereochemically active lone pair. Unlike the analogous carbonyl adducts [Ru(η⁵-indenyl)(PAr₂)(CO)(PPh₃)], these benzonitrile complexes behave as masked sources of the highly reactive planar phosphido complexes [Ru(η⁵-indenyl)(PAr₂)(PPh₃)], which contain a Ru═PAr₂ π bond. This is illustrated by the addition (or cycloaddition) reactions of the benzonitrile adducts with dihydrogen, methyl iodide, and 1-hexene, as well as their thermal decomposition via orthometalation of the PPh₃ ligand. Enthalpies of CO vs NCPh dissociation from the [Ru(η⁵-indenyl)(PR₂)(PPh₃)] fragments (R = alkyl, aryl) have been calculated, as has the trajectory of addition of H₂ to the model planar phosphido complex [Ru(η⁵-indenyl)(PMe₂)(PMe₃)]. The latter study shows the intermediacy of an η²-H₂ adduct, [Ru(η⁵-indenyl)(PAr₂)(η²-H₂)(PPh₃)], in the formation of [RuH(η⁵-indenyl)(HPMe₂)(PMe₃)], a further indication of the importance of the variable binding modes of the terminal phosphido ligand in this system.