Matches in SemOpenAlex for { <https://semopenalex.org/work/W134562474> ?p ?o ?g. }
Showing items 1 to 83 of
83
with 100 items per page.
- W134562474 abstract "This thesis describes the incorporation of carbohydrate groups in thiourea, 1, or iminophosphorane, 2, ligands. Several carbohydrate acyl thioureas, 3, were synthesised from the reaction of protected and unprotected D‐glucosamine with acyl isothiocyanates, RCONCS. Internal hydrogen‐bonding forms a planar six‐membered ring, which locks the thiourea into an Z,E,Z‐anti conformation as shown by 1H NMR spectroscopy and confirmed by X‐ray structure determination of two examples. As neutral ligands to Rh(III), Rh(I), Ru(II), Pd(II), Pt(II) and Au(I) they bond through the sulfur atom with retention of the six‐membered ring and the Z,E,Z‐anti conformation. This was confirmed by two X‐ray structure determinations on Rh(III) and Pd(II) examples which also showed the new hydrogen‐bond formed by HN2 to a halide on the metal. Deprotonation of the ligands 3 with NaOAc gave anionic species which formed bidentate chelating complexes with metals. When attached to Rh(III), Ru(II) or with two thiourea bonding to Pd(II) it forms a four‐membered ring through the S and N2 atoms which retains the hydrogen‐bond. If Rh(I) or (C,Ndimethylbenzylamine‐ Pd) is used a six‐membered ring is formed through the S and O atoms which disrupts the hydrogen‐bond. This disruption of the hydrogenbond is apparent from the chemical shift of HN1. For examples where coordination led to a chiral metal complex (e.g. for Cp*RhCl(N,S‐thiourea)) NMR measurements showed that the natural chirality of the ligand did not provide any selectivity with equal proportions of the two diastereoisomers formed.Iminophosphoranes were produced by the reaction of protected sugar azides with phosphines via the Staudinger reaction. Cyclometalated complexes, 4, could not be formed directly which an X‐ray structure determination suggested was because of steric crowding of the nitrogen. An indirect transmetalation route was developed where the sugar azides were reacted with the mercurated diphosphine, Hg(2‐C₆H₄PPh₂)₂, and the resulting iminophosphoranes transmetalated with [NMe₄][AuCl₄] to produce cyclometalated Au(III) dichloride complexes. Two X‐ray structure determinations showed that the five‐membered metalocyclic ring was in an envelope conformation. The chlorides were labile and able to be displaced by PPh3 and thiosalicylic acid.A series of N‐sugar and N‐phenyl iminophosphorane Au(III) complexes were shown to catalyse the addition of 2‐methyl furan to methyl vinyl ketone." @default.
- W134562474 created "2016-06-24" @default.
- W134562474 creator A5002691922 @default.
- W134562474 date "2011-01-01" @default.
- W134562474 modified "2023-09-23" @default.
- W134562474 title "Asymmetric Ligands Derived from Carbohydrates" @default.
- W134562474 hasPublicationYear "2011" @default.
- W134562474 type Work @default.
- W134562474 sameAs 134562474 @default.
- W134562474 citedByCount "0" @default.
- W134562474 crossrefType "dissertation" @default.
- W134562474 hasAuthorship W134562474A5002691922 @default.
- W134562474 hasConcept C112887158 @default.
- W134562474 hasConcept C115624301 @default.
- W134562474 hasConcept C116569031 @default.
- W134562474 hasConcept C118629725 @default.
- W134562474 hasConcept C121332964 @default.
- W134562474 hasConcept C124668440 @default.
- W134562474 hasConcept C145148216 @default.
- W134562474 hasConcept C170493617 @default.
- W134562474 hasConcept C178516000 @default.
- W134562474 hasConcept C178790620 @default.
- W134562474 hasConcept C185592680 @default.
- W134562474 hasConcept C20621625 @default.
- W134562474 hasConcept C2780378348 @default.
- W134562474 hasConcept C2780538656 @default.
- W134562474 hasConcept C32909587 @default.
- W134562474 hasConcept C52703039 @default.
- W134562474 hasConcept C55493867 @default.
- W134562474 hasConcept C62520636 @default.
- W134562474 hasConcept C66974803 @default.
- W134562474 hasConcept C71240020 @default.
- W134562474 hasConcept C7602139 @default.
- W134562474 hasConcept C8010536 @default.
- W134562474 hasConceptScore W134562474C112887158 @default.
- W134562474 hasConceptScore W134562474C115624301 @default.
- W134562474 hasConceptScore W134562474C116569031 @default.
- W134562474 hasConceptScore W134562474C118629725 @default.
- W134562474 hasConceptScore W134562474C121332964 @default.
- W134562474 hasConceptScore W134562474C124668440 @default.
- W134562474 hasConceptScore W134562474C145148216 @default.
- W134562474 hasConceptScore W134562474C170493617 @default.
- W134562474 hasConceptScore W134562474C178516000 @default.
- W134562474 hasConceptScore W134562474C178790620 @default.
- W134562474 hasConceptScore W134562474C185592680 @default.
- W134562474 hasConceptScore W134562474C20621625 @default.
- W134562474 hasConceptScore W134562474C2780378348 @default.
- W134562474 hasConceptScore W134562474C2780538656 @default.
- W134562474 hasConceptScore W134562474C32909587 @default.
- W134562474 hasConceptScore W134562474C52703039 @default.
- W134562474 hasConceptScore W134562474C55493867 @default.
- W134562474 hasConceptScore W134562474C62520636 @default.
- W134562474 hasConceptScore W134562474C66974803 @default.
- W134562474 hasConceptScore W134562474C71240020 @default.
- W134562474 hasConceptScore W134562474C7602139 @default.
- W134562474 hasConceptScore W134562474C8010536 @default.
- W134562474 hasLocation W1345624741 @default.
- W134562474 hasOpenAccess W134562474 @default.
- W134562474 hasPrimaryLocation W1345624741 @default.
- W134562474 hasRelatedWork W1964850698 @default.
- W134562474 hasRelatedWork W1973304064 @default.
- W134562474 hasRelatedWork W1980610553 @default.
- W134562474 hasRelatedWork W1987527111 @default.
- W134562474 hasRelatedWork W2004376271 @default.
- W134562474 hasRelatedWork W2009285537 @default.
- W134562474 hasRelatedWork W2035754051 @default.
- W134562474 hasRelatedWork W2037849656 @default.
- W134562474 hasRelatedWork W2053414500 @default.
- W134562474 hasRelatedWork W2057538912 @default.
- W134562474 hasRelatedWork W2118787565 @default.
- W134562474 hasRelatedWork W2138366418 @default.
- W134562474 hasRelatedWork W2165345951 @default.
- W134562474 hasRelatedWork W2199993115 @default.
- W134562474 hasRelatedWork W2748058921 @default.
- W134562474 hasRelatedWork W2967520703 @default.
- W134562474 hasRelatedWork W3122267782 @default.
- W134562474 hasRelatedWork W971201791 @default.
- W134562474 hasRelatedWork W193421319 @default.
- W134562474 hasRelatedWork W2052023817 @default.
- W134562474 isParatext "false" @default.
- W134562474 isRetracted "false" @default.
- W134562474 magId "134562474" @default.
- W134562474 workType "dissertation" @default.