FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2006788124> ?p ?o ?g. }

• W2006788124 endingPage "2042" @default.
• W2006788124 startingPage "2035" @default.
• W2006788124 abstract "The dimetal-hexaalkoxides of molybdenum and tungsten (MM) [1a : W2(OtBu)6, 1b : W2(OCH2tBu)6, 1c : Mo2(OtBu)6, 1d : Mo2(OtPr)6, 1e : Mo2(OCH2tBu)6] react reversibly with one equivalent of cyanide ion as its nBu4N salt in non-polar media to form mono-adducts of formula [nBu4N]+[M2(OR)6(CN)]− (2a–e). The spectroscopic data are consistent with the presence of a μ-CN moiety which interacts predominantly as a σ-donor, but do not discount alternative structures which exhibit rapid fluxionality. Addition of a second equivalent (or more) of nBu4NCN leads to the reversible formation of 1,2-diadducts of formula [nBu4N]2+[M2(OR)6(CN)2]2− (3a, 3b, 3d, 3e). Coordination of a second equivalent of cyanide is significantly less favorable than the first so that the consecutive equilibria may be measured. Determination of Keq for the equilibrium M2(OR)6+CN− ⇋ [M2(OR)6(CN)]− allows the first quantitative comparison of the Lewis acidity of the reactive dimetal hexaalkoxides. The identity of the metal and steric factors have a significant effect as shown by the following data: for the formation of 2a, ΔH° = − 11.2(1) kcal mol−1, ΔS° = − 18.6(7) eu; 2c, ΔH° = − 8.8(1) kcal mol−1, ΔS° = − 18.8(9) eu; 2d, ΔH° = − 10.5(1) kcal mol−1, ΔS° = − 18.0(8) eu. Complexes 2b and 2e showed no signs of dissociation under similar conditions and thermodynamic parameters associated with their formation may only be estimated (ΔH° = − 16.9 kcal mol−1, ΔS° = − 18.5 eu and ΔH° = − 13.5 kcal mol−1, ΔS° = − 18.5 eu respectively). At high temperatures the equilibrium becomes fast relative to the NMR time scale for molybdenum, and this allows an estimation of the rate of dissociation by dynamic lineshape analysis. For [Mo2(OtBu)6 (CN)]− (2c) ΔH‡ = 22.0(5) kcal mol−1, ΔS‡ = 13.5(8) eu while for [Mo2(OCH2tBu)6 (CN)]− (2e) ΔH‡ = 22.2(5) kcal mol−1, ΔS‡ = 13.9(8) eu. Line broadening was not observed for the tungsten alkoxide complexes 2a–b consistent with the greater thermodynamic strength of the W2(CN) bond (ΔΔH° = − 2.4 kcal mol−1). The second equilibrium [M2(OR)6(μ-CN)]− + CN− ⇋ [M2(OR)6(CN)2]2− shows a similar dependence on the nature of the metal and alkoxide: for formation of 3a, ΔH° = − 9.3(5) kcal mol−1, ΔS° = − 29(2) eu; for 3e, ΔH° = − 11.6(5) kcal mol−1, ΔS° = − 29(2) eu. In contrast, 3c was not detected under any conditions (ΔH° = − 6.9 kcal mol−1, ΔS° = − 29.2 eu, estimated) while 3b was undissociated under similar conditions (ΔH° = − 15.0 kcal mol−1, ΔS° = − 29.2 eu, estimated)." @default.
• W2006788124 created "2016-06-24" @default.
• W2006788124 creator A5004096016 @default.
• W2006788124 creator A5036719498 @default.
• W2006788124 date "1994-07-01" @default.
• W2006788124 modified "2023-09-27" @default.
• W2006788124 title "Coordination chemistry of complexes with metalmetal multiple bonds: Reversible coordination of cyanide ion by dimolybdenum and ditungsten hexaalkoxides" @default.
• W2006788124 cites W1967288355 @default.
• W2006788124 cites W1990695488 @default.
• W2006788124 cites W2044712518 @default.
• W2006788124 cites W2054924137 @default.
• W2006788124 cites W2057319521 @default.
• W2006788124 cites W2067425403 @default.
• W2006788124 cites W2122726318 @default.
• W2006788124 cites W2952378141 @default.
• W2006788124 cites W3136824478 @default.
• W2006788124 cites W49029818 @default.
• W2006788124 doi "https://doi.org/10.1016/s0277-5387(00)83486-5" @default.
• W2006788124 hasPublicationYear "1994" @default.
• W2006788124 type Work @default.
• W2006788124 sameAs 2006788124 @default.
• W2006788124 citedByCount "13" @default.
• W2006788124 countsByYear W20067881242018 @default.
• W2006788124 crossrefType "journal-article" @default.
• W2006788124 hasAuthorship W2006788124A5004096016 @default.
• W2006788124 hasAuthorship W2006788124A5036719498 @default.
• W2006788124 hasConcept C102931765 @default.
• W2006788124 hasConcept C108204754 @default.
• W2006788124 hasConcept C147789679 @default.
• W2006788124 hasConcept C155647269 @default.
• W2006788124 hasConcept C161790260 @default.
• W2006788124 hasConcept C163638829 @default.
• W2006788124 hasConcept C178790620 @default.
• W2006788124 hasConcept C179104552 @default.
• W2006788124 hasConcept C185592680 @default.
• W2006788124 hasConcept C201194858 @default.
• W2006788124 hasConcept C2776568683 @default.
• W2006788124 hasConcept C2778455166 @default.
• W2006788124 hasConcept C544153396 @default.
• W2006788124 hasConcept C549387045 @default.
• W2006788124 hasConcept C68913812 @default.
• W2006788124 hasConcept C71240020 @default.
• W2006788124 hasConcept C8010536 @default.
• W2006788124 hasConcept C84264389 @default.
• W2006788124 hasConceptScore W2006788124C102931765 @default.
• W2006788124 hasConceptScore W2006788124C108204754 @default.
• W2006788124 hasConceptScore W2006788124C147789679 @default.
• W2006788124 hasConceptScore W2006788124C155647269 @default.
• W2006788124 hasConceptScore W2006788124C161790260 @default.
• W2006788124 hasConceptScore W2006788124C163638829 @default.
• W2006788124 hasConceptScore W2006788124C178790620 @default.
• W2006788124 hasConceptScore W2006788124C179104552 @default.
• W2006788124 hasConceptScore W2006788124C185592680 @default.
• W2006788124 hasConceptScore W2006788124C201194858 @default.
• W2006788124 hasConceptScore W2006788124C2776568683 @default.
• W2006788124 hasConceptScore W2006788124C2778455166 @default.
• W2006788124 hasConceptScore W2006788124C544153396 @default.
• W2006788124 hasConceptScore W2006788124C549387045 @default.
• W2006788124 hasConceptScore W2006788124C68913812 @default.
• W2006788124 hasConceptScore W2006788124C71240020 @default.
• W2006788124 hasConceptScore W2006788124C8010536 @default.
• W2006788124 hasConceptScore W2006788124C84264389 @default.
• W2006788124 hasIssue "13" @default.
• W2006788124 hasLocation W20067881241 @default.
• W2006788124 hasOpenAccess W2006788124 @default.
• W2006788124 hasPrimaryLocation W20067881241 @default.
• W2006788124 hasRelatedWork W1971947695 @default.
• W2006788124 hasRelatedWork W2006788124 @default.
• W2006788124 hasRelatedWork W2038804434 @default.
• W2006788124 hasRelatedWork W2054635170 @default.
• W2006788124 hasRelatedWork W2071560566 @default.
• W2006788124 hasRelatedWork W2076110975 @default.
• W2006788124 hasRelatedWork W2086609181 @default.
• W2006788124 hasRelatedWork W2105713502 @default.
• W2006788124 hasRelatedWork W2256202378 @default.
• W2006788124 hasRelatedWork W2940844273 @default.
• W2006788124 hasVolume "13" @default.
• W2006788124 isParatext "false" @default.
• W2006788124 isRetracted "false" @default.
• W2006788124 magId "2006788124" @default.
• W2006788124 workType "article" @default.