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SYNTHESIS, STRUCTURE AND HYDROGENATION OF ETA-3-BENZYL DIPHOSPHINE COMPLEXES OF RHODIUM AND IRIDIUM

TitleSYNTHESIS, STRUCTURE AND HYDROGENATION OF ETA-3-BENZYL DIPHOSPHINE COMPLEXES OF RHODIUM AND IRIDIUM
Publication TypeJournal Article
Year of Publication1993
AuthorsFryzuk, MD, McConville, DH, Rettig, SJ
JournalJournal of Organometallic Chemistry
Volume445
Pagination245-256
Date PublishedFeb
Type of ArticleArticle
ISBN Number0022-328X
KeywordsBINUCLEAR, BRIDGING ALKENYL, CATALYTIC-HYDROGENATION, CHEMISTRY, DIHYDROGEN, Hydrides, OXIDATIVE-ADDITION, RAY CRYSTAL-STRUCTURE, REACTIVITY, RHRE(CO)4(PH2PCH2PPH2)2
Abstract

{The preparation of(COD)Rh(eta3-CH2Ph) is described starting from [(COD)Rh]2(mu-Cl)2 by the addition of either Zn(CH2Ph), or Mg(CH2Ph)2(THF)2. The addition of the bulky chelating diphosphines tBu2P(CH2)3PtBu2, iPr2P(CH2)3PiPr2, iPr2P(CH2)2PiPr2, iPr2PCH2PiPr2 and Cy2PCH2PCy2 to (COD)Rh(eta3-CH2Ph) yields the coordinatively unsaturated, four-coordinate rhodium complexes of the form P2Rh(eta3-CH2Ph). Iridium complexes of the form P2Ir(eta3-CH2Ph)(where P2 = tBu2P(CH2)3PtBu, and iPr2P(CH2)3PiPr2) can be prepared from [P2Ir]2(mu-Cl), and Zn(CH2Ph)2 or Mg(CHPh)2(THF)2. Reaction of the benzyl complexes with H-2 (1 atM) yields binuclear hydride derivatives of varying composition depending on the chelate ring size of the coordinated diphosphine. For the diphosphines with only a single methylene in the backbone, binuclear hexahydride complexes are formed in which the diphosphine is binucleating. The X-ray structure of {iPr2P(CH22)3PiPr2}Rh(eta3-CH2Ph) shows a square planar geometry about rhodium with alternating single and double bonds in the eta3-coordinated benzyl fragment. Crystals of (1,3-bis(diiso-propylphosphino)propane}rhodium(eta3-benzyl) are monoclinic

URL<Go to ISI>://A1993KR22100035