Diastereomers of CpRh{C(O)Me}(P*)I, (P* (TBOND) (S)-Ph(,2)PNHCH(Me)Ph), have been prepared and separated. Decarbonylation with AgBF(,4) gave a single diastereomer of CpRhMe(CO)(P*)(.)BF(,4) and subsequent treatment of the salt with anions likewise gave single isomers of CpRh{C(O)Me}(P*)X (X = Cl, Br, I, SCN, NCS). The high stereospecificity of these transformations is attributed to the ability of the acyl ligand to undergo stereospecific reversible decarbonylation such that the methyl group occupies the site vacated by the iodide ligand, i.e., inversion. Addition of N(,3)('-) and MeO('-) to the salt resulted in the stereospecific formation of CpRhMe(P*)X' (X' = NCO, COOMe). Metathesis of CpRh{C(O)Me}(P*)Cl with I('-) proceeded with retention of configuration at rhodium. / The chiral complexes (1-C(,9)H(,6)Cl)Rh(COD), (COD (TBOND) 1,5-cyclooctadiene), and (1-C(,9)H(,6)X)Mn(CO)(,3), (X = Cl, Br, I) have been synthesized via diazoindene insertion. Only the pentahapto bonding mode has been detected for these complexes. / Photochemical and chemical decarbonylation of trans-CpFe(CO)(,2){C(O)CH=CHR}, (R = Ph, Me), proceeded with retention of geometry about the double bond to give trans-CpFe(CO)(,2){CH=CHR}.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.68632 |
| Date | January 1981 |
| Creators | Quinn, Susan M. (Susan Mary) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 000139376, proquestno: AAINK58163, Theses scanned by UMI/ProQuest. |
Page generated in 0.0056 seconds