Activation of metal hydride complexes by tri-tert-butylphosphine-platinum and -palladium groups

Richard D. Adams, Burjor Captain, Eszter Trufan, Lei Zhu

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

The compounds HM(CO)4SnPh3, M = Os (10), Ru (11) are activated in the presence of Pt-(PBut3)2 and Pd(PBut3)2 toward the insertion of PhC 2H into the M-H bond. The compounds PtOs(CO)4-(SnPh 3)(PBut3)[μ-HCC(H)Ph], 12, and PtOs(CO) 4(SnPh3)(PBut3)[μ-H 2CCPh], 13, were obtained from the reaction of 10 with PhC 2H in the presence of Pt(PBut3)2. Compounds 12 and 13 are isomers containing alkenyl ligands formed by the insertion of the PhC2H molecule into the Os-H bond at both the substituted and unsubstituted carbon atoms of the alkyne. Both compounds contain a Pt(PBut3) group that is bonded to the osmium atom and a bridging alkenyl ligand that is π-bonded to the osmium atom. The reaction of 11 with PhC2H in the presence of Pt(PBut 3)2 yielded the products PtRu(CO)4(SnPh 3)(PBut3)[μ-HC2(H)Ph], 14, and PtRu(CO)4(SnPh3)(PBut3)[μ-H 2C2Ph], 15, which are also isomers similar to 12 and 13. The reaction of 11 with PhC2H in the presence of Pd(PBu t3)2 yielded the product PdRu(CO) 4(SnPh3)(PBut3)[μ-H 2C2Ph], 16. Compound 16 contains a Pd(PBut 3) group bonded to the ruthenium atom and a bridging H 2C2Ph ligand that is π-bonded to the palladium atom. Compound 10 reacted with Pt(PBut3)2 in the absence of PhC2H to yield the compound PtOs(CO)4(SnPh 3)(PBut3)(μ-H), 17. Compound 17 is a Pt(PBut3) adduct of 10. It contains a Pt-Os bond with a bridging hydrido ligand. Compound 17 reacted with PhC2H to yield 12. Compound 12 reacted with PhC2H to yield the compound PtOs(CO) 3(SnPh3)(PBut3)[μ-HCC(Ph)C(H)C(H) Ph], 18. Compound 18 contains a bridging 2,4-diphenylbutadienyl ligand, HCC(Ph)C(H)C(H)Ph, that is π-bonded to the osmium atom and σ-bonded to the platinum atom. Fenkse-Hall molecular orbitals of 17 were calculated. The LUMO of 17 exhibits an empty orbital on the platinum atom that appears to be the most likely site for PhC2H addition prior to its insertion into the Os-H bond.

Original languageEnglish (US)
Pages (from-to)7545-7556
Number of pages12
JournalJournal of the American Chemical Society
Volume129
Issue number24
DOIs
StatePublished - Jun 20 2007
Externally publishedYes

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Activation of metal hydride complexes by tri-tert-butylphosphine-platinum and -palladium groups'. Together they form a unique fingerprint.

  • Cite this