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Interactions of Rh(III)-dihydrido-bis(phosphine) complexes with semicarbazones

TitleInteractions of Rh(III)-dihydrido-bis(phosphine) complexes with semicarbazones
Publication TypeJournal Article
Year of Publication2005
AuthorsEzhova, MB, Patrick, BO, Sereviratne, KN, James, BR, Waller, FJ, Ford, ME
JournalInorganic Chemistry
Volume44
Pagination1482-1491
Date PublishedMar
Type of ArticleArticle
ISBN Number0020-1669
KeywordsBENZALDEHYDE SEMICARBAZONE, CATALYST, COMPLEXES, CRYSTAL-STRUCTURES, DIHYDRIDO COMPLEXES, HYDROGENATION, LIGANDS, MOLECULAR-STRUCTURES, REFINEMENT, rhodium, UNPRECEDENTED CHEMICAL TRANSFORMATION
Abstract

Interaction of cis, trans, cis-[Rh(H)(2)(PR3)(2)(acetone)(2)] PF6 complexes (R = aryl or R-3 = Ph2Me, Ph2Et) under H-2 with E-semicarbazones gives the Rh(III)-dihydrido-bis(phosphine)-semicarbazone species cis, trans-[Rh(H)(2)(PR3)(2)-{R’(R")C=N-N(H)CONH2}]PF6, where R’ and R" are Ph, Et, or Me. The complexes are generally characterized by elemental analysis, P-31{H-1} NMR, H-1 NMR, and IR spectroscopies, and MS. X-ray analysis of three PPh3 complexes reveals chelation of E-semicarbazones by the imine-N atom and the carbonyl-O atom. In contrast, the corresponding reaction of [Rh(H)(2)(PPhMe2)(2)(acetone)(2)]PF6 with acelophenone semicarbazone gives the orthometalated-semicarbazone species cis-[RhH(PPhMe2)(2){o-C6H4(Me)C=N-N(H)CONH2}]PF6. The X-ray structure of E-propophenone semicarbazone is also reported. Rhodium-catalyzed, homogeneous hydrogenation of semicarbazones was not observed even at 40 atm H-2.

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