FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2005058045> ?p ?o ?g. }

• W2005058045 endingPage "348" @default.
• W2005058045 startingPage "333" @default.
• W2005058045 abstract "First order rate constants have been determined for the loss of tritium from tritiated germanium hydrides in MeOH/MeONa at 20–40°C. The rate constant for Ph3GeT (T = 3H) is greater than that for exchange at the 9-position of fluorene under similar conditions. Values of krel, the rate relative to that for Ph3-GeH, for (XC6H4)3GeT compounds at 30°C are: (X =) m-Cl, 380; p-Cl, 71; m-Me, 0.48; p-Me, 0.078; o-Me, 0.081; p-OMe, 0.025; o-Me, 0.018, and there is a good linear correlation between log krel and σ. For the compounds (XC6H4)-Ph2GeT the values of krel are (X =) p-NO2, 1280; p-CN, 680; m-Cl, 10; and p-F, 1.1, and a plot of log krel against σ− constants is much better than that against σ constants. The results imply that there is substantial delocalization of charge from the anionic germanium centre into the aromatic rings, and thus na important degree of (pp)π bonding between the germanium atom and these rings in the anion. The rates of exchange fall on going from Ph3GeT to Ph2GeHT, to PhGeH2T (the values of krel being 1, 0.11, and ca. 0.015 respectively), implying an order of kinetic acidities opposite to the reported order of equilibrium acidities in liquid ammonia. Replacement of Ph by Et groups also leads to a fall in kinetic acidity, values of krel for EtPh2GeT and Et3GeT being 6 × 10−2 and ca. 3 × 10−3, respectively. Solvolysis, involving generation of hydrogen, is significant for PhGeH3 under the reaction conditions, and important for Et3GeH. The value of the inverse solvent isotope effect, kMeOD/kMeOH is ca. 1.7 for both Ph3GeT and (m-ClC6H4)3 GeT at 20°C. This value, and the activation parameters determined for some of the (XC6H4)3GeT compounds are consistent with a transition state for the rate-determining step in which the hydrogen is roughly half transferred from germanium to methoxide ion, with partial liberation of the methanol molecules initially solvating the latter." @default.
• W2005058045 created "2016-06-24" @default.
• W2005058045 creator A5010685518 @default.
• W2005058045 creator A5039185826 @default.
• W2005058045 date "1979-09-01" @default.
• W2005058045 modified "2023-10-11" @default.
• W2005058045 title "Base-catalysed hydrogen-exchange between organogermanium hydrides and methanol" @default.
• W2005058045 cites W1573435916 @default.
• W2005058045 cites W184276210 @default.
• W2005058045 cites W1964997463 @default.
• W2005058045 cites W1965350399 @default.
• W2005058045 cites W1972072086 @default.
• W2005058045 cites W1981395395 @default.
• W2005058045 cites W1997361049 @default.
• W2005058045 cites W2003451960 @default.
• W2005058045 cites W2011436143 @default.
• W2005058045 cites W2017679285 @default.
• W2005058045 cites W2027707581 @default.
• W2005058045 cites W2041007710 @default.
• W2005058045 cites W2068594964 @default.
• W2005058045 cites W2072624193 @default.
• W2005058045 cites W2076701682 @default.
• W2005058045 cites W2089148775 @default.
• W2005058045 cites W2129618418 @default.
• W2005058045 cites W2169510086 @default.
• W2005058045 cites W2301692248 @default.
• W2005058045 cites W2333047244 @default.
• W2005058045 cites W2949405393 @default.
• W2005058045 cites W4242686813 @default.
• W2005058045 cites W1987274012 @default.
• W2005058045 doi "https://doi.org/10.1016/s0022-328x(00)94078-6" @default.
• W2005058045 hasPublicationYear "1979" @default.
• W2005058045 type Work @default.
• W2005058045 sameAs 2005058045 @default.
• W2005058045 citedByCount "16" @default.
• W2005058045 countsByYear W20050580452023 @default.
• W2005058045 crossrefType "journal-article" @default.
• W2005058045 hasAuthorship W2005058045A5010685518 @default.
• W2005058045 hasAuthorship W2005058045A5039185826 @default.
• W2005058045 hasConcept C109057382 @default.
• W2005058045 hasConcept C121332964 @default.
• W2005058045 hasConcept C148898269 @default.
• W2005058045 hasConcept C155647269 @default.
• W2005058045 hasConcept C178790620 @default.
• W2005058045 hasConcept C185592680 @default.
• W2005058045 hasConcept C2777706827 @default.
• W2005058045 hasConcept C2779293432 @default.
• W2005058045 hasConcept C2779607525 @default.
• W2005058045 hasConcept C62520636 @default.
• W2005058045 hasConcept C93391505 @default.
• W2005058045 hasConcept C94412978 @default.
• W2005058045 hasConceptScore W2005058045C109057382 @default.
• W2005058045 hasConceptScore W2005058045C121332964 @default.
• W2005058045 hasConceptScore W2005058045C148898269 @default.
• W2005058045 hasConceptScore W2005058045C155647269 @default.
• W2005058045 hasConceptScore W2005058045C178790620 @default.
• W2005058045 hasConceptScore W2005058045C185592680 @default.
• W2005058045 hasConceptScore W2005058045C2777706827 @default.
• W2005058045 hasConceptScore W2005058045C2779293432 @default.
• W2005058045 hasConceptScore W2005058045C2779607525 @default.
• W2005058045 hasConceptScore W2005058045C62520636 @default.
• W2005058045 hasConceptScore W2005058045C93391505 @default.
• W2005058045 hasConceptScore W2005058045C94412978 @default.
• W2005058045 hasIssue "2" @default.
• W2005058045 hasLocation W20050580451 @default.
• W2005058045 hasOpenAccess W2005058045 @default.
• W2005058045 hasPrimaryLocation W20050580451 @default.
• W2005058045 hasRelatedWork W1972861302 @default.
• W2005058045 hasRelatedWork W2002199493 @default.
• W2005058045 hasRelatedWork W2009863590 @default.
• W2005058045 hasRelatedWork W2059820162 @default.
• W2005058045 hasRelatedWork W2066678084 @default.
• W2005058045 hasRelatedWork W2127502572 @default.
• W2005058045 hasRelatedWork W2135428989 @default.
• W2005058045 hasRelatedWork W2950116719 @default.
• W2005058045 hasRelatedWork W2950493987 @default.
• W2005058045 hasRelatedWork W4249396460 @default.
• W2005058045 hasVolume "177" @default.
• W2005058045 isParatext "false" @default.
• W2005058045 isRetracted "false" @default.
• W2005058045 magId "2005058045" @default.
• W2005058045 workType "article" @default.