FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2009035461> ?p ?o ?g. }

• W2009035461 endingPage "15423" @default.
• W2009035461 startingPage "15412" @default.
• W2009035461 abstract "Variable temperature equilibrium studies were used to derive thermodynamic data for formation of η1 nitrile complexes with Mo(N[tBu]Ar)3, 1. (1-AdamantylCN = AdCN: ΔHo = −6 ± 2 kcal mol−1, ΔSo = −20 ± 7 cal mol−1 K−1. C6H5CN = PhCN: ΔHo = −14.5 ± 1.5 kcal mol−1, ΔSo = −40 ± 5 cal mol−1 K−1. 2,4,6-(H3C)3C6H2CN = MesCN: ΔHo = −15.4 ± 1.5 kcal mol−1, ΔSo = −52 ± 5 cal mol−1 K−1.) Solution calorimetric studies show that the enthalpy of formation of 1-[η2-NCNMe2] is more exothermic (ΔHo = −22.0 ± 1.0 kcal mol−1). Rate and activation parameters for η1 binding of nitriles were measured by stopped flow kinetic studies (AdCN: ΔHon‡ = 5 ± 1 kcal mol−1, ΔSon‡ = −28 ± 5 cal mol−1 K−1; PhCN: ΔHon‡ = 5.2 ± 0.2 kcal mol−1, ΔSon‡ = −24 ± 1 cal mol−1 K−1; MesCN: ΔHon‡ = 5.0 ± 0.3 kcal mol−1, ΔSon‡ = −26 ± 1 cal mol−1 K−1). Binding of Me2NCN was observed to proceed by reversible formation of an intermediate complex 1-[η1-NCNMe2] which subsequently forms 1-[η2-NCNMe2]: ΔH‡k1 = 6.4 ± 0.4 kcal mol−1, ΔS‡k1 = −18 ± 2 cal mol−1 K−1, and ΔH‡k2 = 11.1 ± 0.2 kcal mol−1, ΔS‡k2 = −7.5 ± 0.8 cal mol−1 K−1. The oxidative addition of PhSSPh to 1-[η1-NCPh] is a rapid second-order process with activation parameters: ΔH‡ = 6.7 ± 0.6 kcal mol−1, ΔS‡ = −27 ± 4 cal mol−1 K−1. The oxidative addition of PhSSPh to 1-[η2-NCNMe2] also followed a second-order rate law but was much slower: ΔH‡ = 12.2 ± 1.5 kcal mol−1 and ΔS‡ = −25.4 ± 5.0 cal mol−1 K−1. The crystal structure of 1-[η1-NC(SPh)NMe2] is reported. Trapping of in situ generated 1-[η1-NCNMe2] by PhSSPh was successful at low temperatures (−80 to −40 °C) as studied by stopped flow methods. If 1-[η1-NCNMe2] is not intercepted before isomerization to 1-[η2-NCNMe2] no oxidative addition occurs at low temperatures. The structures of key intermediates have been studied by density functional theory, confirming partial radical character of the carbon atom in η1-bound nitriles. A complete reaction profile for reversible ligand binding, η1 to η2 isomerization, and oxidative addition of PhSSPh has been assembled and gives a clear picture of ligand reactivity as a function of hapticity in this system." @default.
• W2009035461 created "2016-06-24" @default.
• W2009035461 creator A5004212083 @default.
• W2009035461 creator A5009076122 @default.
• W2009035461 creator A5009866988 @default.
• W2009035461 creator A5021833998 @default.
• W2009035461 creator A5031493178 @default.
• W2009035461 creator A5038730132 @default.
• W2009035461 creator A5040222176 @default.
• W2009035461 creator A5047652105 @default.
• W2009035461 creator A5070410935 @default.
• W2009035461 creator A5071702193 @default.
• W2009035461 creator A5075414167 @default.
• W2009035461 creator A5084287341 @default.
• W2009035461 date "2009-10-01" @default.
• W2009035461 modified "2023-10-17" @default.
• W2009035461 title "Coordination-Mode Control of Bound Nitrile Radical Complex Reactivity: Intercepting End-on Nitrile−Mo(III) Radicals at Low Temperature" @default.
• W2009035461 cites W1965607988 @default.
• W2009035461 cites W1968281881 @default.
• W2009035461 cites W1973022773 @default.
• W2009035461 cites W1983787579 @default.
• W2009035461 cites W1984577830 @default.
• W2009035461 cites W1986534520 @default.
• W2009035461 cites W1997286713 @default.
• W2009035461 cites W1999659754 @default.
• W2009035461 cites W2001240769 @default.
• W2009035461 cites W2002389669 @default.
• W2009035461 cites W2004957923 @default.
• W2009035461 cites W2012380338 @default.
• W2009035461 cites W2012748536 @default.
• W2009035461 cites W2012956432 @default.
• W2009035461 cites W2013224988 @default.
• W2009035461 cites W2016566647 @default.
• W2009035461 cites W2021713602 @default.
• W2009035461 cites W2025119422 @default.
• W2009035461 cites W2033550557 @default.
• W2009035461 cites W2035215003 @default.
• W2009035461 cites W2040562836 @default.
• W2009035461 cites W2040742919 @default.
• W2009035461 cites W2043614925 @default.
• W2009035461 cites W2050097723 @default.
• W2009035461 cites W2065998871 @default.
• W2009035461 cites W2077107026 @default.
• W2009035461 cites W2079202542 @default.
• W2009035461 cites W2082434005 @default.
• W2009035461 cites W2089072541 @default.
• W2009035461 cites W2089867192 @default.
• W2009035461 cites W2092462649 @default.
• W2009035461 cites W2102249406 @default.
• W2009035461 cites W2133081041 @default.
• W2009035461 cites W2133334675 @default.
• W2009035461 cites W2143084823 @default.
• W2009035461 cites W2319844438 @default.
• W2009035461 cites W2949503369 @default.
• W2009035461 cites W2949846648 @default.
• W2009035461 doi "https://doi.org/10.1021/ja905849a" @default.
• W2009035461 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/19919164" @default.
• W2009035461 hasPublicationYear "2009" @default.
• W2009035461 type Work @default.
• W2009035461 sameAs 2009035461 @default.
• W2009035461 citedByCount "12" @default.
• W2009035461 countsByYear W20090354612013 @default.
• W2009035461 countsByYear W20090354612017 @default.
• W2009035461 countsByYear W20090354612019 @default.
• W2009035461 countsByYear W20090354612023 @default.
• W2009035461 crossrefType "journal-article" @default.
• W2009035461 hasAuthorship W2009035461A5004212083 @default.
• W2009035461 hasAuthorship W2009035461A5009076122 @default.
• W2009035461 hasAuthorship W2009035461A5009866988 @default.
• W2009035461 hasAuthorship W2009035461A5021833998 @default.
• W2009035461 hasAuthorship W2009035461A5031493178 @default.
• W2009035461 hasAuthorship W2009035461A5038730132 @default.
• W2009035461 hasAuthorship W2009035461A5040222176 @default.
• W2009035461 hasAuthorship W2009035461A5047652105 @default.
• W2009035461 hasAuthorship W2009035461A5070410935 @default.
• W2009035461 hasAuthorship W2009035461A5071702193 @default.
• W2009035461 hasAuthorship W2009035461A5075414167 @default.
• W2009035461 hasAuthorship W2009035461A5084287341 @default.
• W2009035461 hasConcept C121332964 @default.
• W2009035461 hasConcept C124815738 @default.
• W2009035461 hasConcept C139066938 @default.
• W2009035461 hasConcept C142724271 @default.
• W2009035461 hasConcept C147789679 @default.
• W2009035461 hasConcept C155647269 @default.
• W2009035461 hasConcept C178790620 @default.
• W2009035461 hasConcept C185592680 @default.
• W2009035461 hasConcept C204787440 @default.
• W2009035461 hasConcept C2776910235 @default.
• W2009035461 hasConcept C2779240715 @default.
• W2009035461 hasConcept C3288061 @default.
• W2009035461 hasConcept C45119746 @default.
• W2009035461 hasConcept C71240020 @default.
• W2009035461 hasConcept C71924100 @default.
• W2009035461 hasConcept C8010536 @default.
• W2009035461 hasConcept C95121573 @default.
• W2009035461 hasConcept C97355855 @default.
• W2009035461 hasConceptScore W2009035461C121332964 @default.
• W2009035461 hasConceptScore W2009035461C124815738 @default.

• next