FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2078981325> ?p ?o ?g. }

• W2078981325 endingPage "1881" @default.
• W2078981325 startingPage "1867" @default.
• W2078981325 abstract "The X-ray structures of three metal alkyne complexes are presented: Ir(PMe2 Ph)3(MeC2Me)+, M(CO)4(F3CC2CF3) (M = Ru, Os). The iridium(I) complex adopts an unusual structure (“CS”) which differs notably from that expected for four-coordinate d8 ML4 square-planar complexes. The structure resembles that of a square pyramid, with essentially Cs symmetry, with a short apical MP bond (2.236 vs 2.31 Å for the basal MP bonds), short MC (2.01 Å) and long CC bonds (1.306 Å), which indicate a strong metal—alkyne interaction. The ruthenium(O) and osmium(O) complexes adopt the expected pseudo-octahedral structure. The unusual CS structures, previously reported for cobalt(I) and iron(O) complexes, contrast with the square-planar structure of platinum(II) alkyne complexes. Fluxionality is present in the iridium complex, as well as in those of cobalt, and is attributed to a rapid intramolecular site exchange among inequivalent phosphorus ligands. The iridium complex reacts with additional ligands like alkynes and H2. Extended Hückel calculations are presented to rationalize the structural and reactivity aspects of the whole family of d8 ML3(alkyne) species (M = PtII, IrI, CoI, FeO). It is shown that the four-electron donation of an alkyne ligand is responsible for the unusual CS structure of certain of these ML3(alkyne) species. The alkyne moieties induce a four-electron destabilization in the square-planar structure which is large for diffuse d orbitals such as those of iridium(I), cobalt(I), iron(O), but not of platinum(II). The fluxionality of the complexes is shown to be associated with an easy rotation of the alkyne about the metal—alkyne midpoint, accompanied by a breathing motion of the ML bonds of the ML3 metal fragment. It is shown that unsymmetrical alkynes stabilize a conformation of the complex in which the ligand is turned by 90° with respect to the one presented here. The reactivity towards additional ligands is shown to be associated with the presence of a low-lying LUMO pointing away from the apical bond. Effects of substituents at the alkyne and of ligands at the metal are discussed. It is shown that it is residual four-electron destabilization in M(CO)4(alkyne) complexes which is responsible for the lability of CO ligands and thus for the ligand exchange process." @default.
• W2078981325 created "2016-06-24" @default.
• W2078981325 creator A5005296357 @default.
• W2078981325 creator A5034052449 @default.
• W2078981325 creator A5037210783 @default.
• W2078981325 creator A5042519898 @default.
• W2078981325 creator A5048526000 @default.
• W2078981325 creator A5048930498 @default.
• W2078981325 creator A5050559192 @default.
• W2078981325 creator A5053674642 @default.
• W2078981325 creator A5073811804 @default.
• W2078981325 creator A5091173351 @default.
• W2078981325 date "1990-01-01" @default.
• W2078981325 modified "2023-10-15" @default.
• W2078981325 title "The origin of structural variety of alkyne complexes of d8 metals. An example of structural isomerism" @default.
• W2078981325 cites W1038509922 @default.
• W2078981325 cites W1591863889 @default.
• W2078981325 cites W1828225620 @default.
• W2078981325 cites W1963951169 @default.
• W2078981325 cites W1977955686 @default.
• W2078981325 cites W1982587630 @default.
• W2078981325 cites W2014086473 @default.
• W2078981325 cites W2015275832 @default.
• W2078981325 cites W2024236957 @default.
• W2078981325 cites W2028457395 @default.
• W2078981325 cites W2034270729 @default.
• W2078981325 cites W2034336228 @default.
• W2078981325 cites W2045133953 @default.
• W2078981325 cites W2060776815 @default.
• W2078981325 cites W2073550810 @default.
• W2078981325 cites W2074002313 @default.
• W2078981325 cites W2076902862 @default.
• W2078981325 cites W2078566538 @default.
• W2078981325 cites W2078937181 @default.
• W2078981325 cites W2084760599 @default.
• W2078981325 cites W2090646744 @default.
• W2078981325 cites W2104155769 @default.
• W2078981325 cites W2317925328 @default.
• W2078981325 cites W2321702846 @default.
• W2078981325 cites W2952782087 @default.
• W2078981325 cites W3004865127 @default.
• W2078981325 cites W3146210623 @default.
• W2078981325 cites W937242747 @default.
• W2078981325 doi "https://doi.org/10.1016/s0277-5387(00)83999-6" @default.
• W2078981325 hasPublicationYear "1990" @default.
• W2078981325 type Work @default.
• W2078981325 sameAs 2078981325 @default.
• W2078981325 citedByCount "31" @default.
• W2078981325 countsByYear W20789813252012 @default.
• W2078981325 countsByYear W20789813252013 @default.
• W2078981325 countsByYear W20789813252015 @default.
• W2078981325 countsByYear W20789813252018 @default.
• W2078981325 countsByYear W20789813252022 @default.
• W2078981325 crossrefType "journal-article" @default.
• W2078981325 hasAuthorship W2078981325A5005296357 @default.
• W2078981325 hasAuthorship W2078981325A5034052449 @default.
• W2078981325 hasAuthorship W2078981325A5037210783 @default.
• W2078981325 hasAuthorship W2078981325A5042519898 @default.
• W2078981325 hasAuthorship W2078981325A5048526000 @default.
• W2078981325 hasAuthorship W2078981325A5048930498 @default.
• W2078981325 hasAuthorship W2078981325A5050559192 @default.
• W2078981325 hasAuthorship W2078981325A5053674642 @default.
• W2078981325 hasAuthorship W2078981325A5073811804 @default.
• W2078981325 hasAuthorship W2078981325A5091173351 @default.
• W2078981325 hasConcept C115624301 @default.
• W2078981325 hasConcept C116569031 @default.
• W2078981325 hasConcept C161790260 @default.
• W2078981325 hasConcept C170493617 @default.
• W2078981325 hasConcept C178790620 @default.
• W2078981325 hasConcept C179104552 @default.
• W2078981325 hasConcept C185592680 @default.
• W2078981325 hasConcept C200119971 @default.
• W2078981325 hasConcept C2779012754 @default.
• W2078981325 hasConcept C515602321 @default.
• W2078981325 hasConcept C528581852 @default.
• W2078981325 hasConcept C540285154 @default.
• W2078981325 hasConcept C544153396 @default.
• W2078981325 hasConcept C55493867 @default.
• W2078981325 hasConcept C555196967 @default.
• W2078981325 hasConcept C71240020 @default.
• W2078981325 hasConcept C75079739 @default.
• W2078981325 hasConcept C8010536 @default.
• W2078981325 hasConceptScore W2078981325C115624301 @default.
• W2078981325 hasConceptScore W2078981325C116569031 @default.
• W2078981325 hasConceptScore W2078981325C161790260 @default.
• W2078981325 hasConceptScore W2078981325C170493617 @default.
• W2078981325 hasConceptScore W2078981325C178790620 @default.
• W2078981325 hasConceptScore W2078981325C179104552 @default.
• W2078981325 hasConceptScore W2078981325C185592680 @default.
• W2078981325 hasConceptScore W2078981325C200119971 @default.
• W2078981325 hasConceptScore W2078981325C2779012754 @default.
• W2078981325 hasConceptScore W2078981325C515602321 @default.
• W2078981325 hasConceptScore W2078981325C528581852 @default.
• W2078981325 hasConceptScore W2078981325C540285154 @default.
• W2078981325 hasConceptScore W2078981325C544153396 @default.
• W2078981325 hasConceptScore W2078981325C55493867 @default.
• W2078981325 hasConceptScore W2078981325C555196967 @default.
• W2078981325 hasConceptScore W2078981325C71240020 @default.

• next