FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2896058167> ?p ?o ?g. }

• W2896058167 endingPage "14970" @default.
• W2896058167 startingPage "14958" @default.
• W2896058167 abstract "Solid/gas single-crystal to single-crystal (SC–SC) hydrogenation of appropriate diene precursors forms the corresponding σ-alkane complexes [Rh(Cy2P(CH2)nPCy2)(L)][BArF4] (n = 3, 4) and [RhH(Cy2P(CH2)2(CH)(CH2)2PCy2)(L)][BArF4] (n = 5, L = norbornane, NBA; cyclooctane, COA). Their structures, as determined by single-crystal X-ray diffraction, have cations exhibiting Rh···H–C σ-interactions which are modulated by both the chelating ligand and the identity of the alkane, while all sit in an octahedral anion microenvironment. These range from chelating η2,η2 Rh···H–C (e.g., [Rh(Cy2P(CH2)nPCy2)(η2η2-NBA)][BArF4], n = 3 and 4), through to more weakly bound η1 Rh···H–C in which C–H activation of the chelate backbone has also occurred (e.g., [RhH(Cy2P(CH2)2(CH)(CH2)2PCy2)(η1-COA)][BArF4]) and ultimately to systems where the alkane is not ligated with the metal center, but sits encapsulated in the supporting anion microenvironment, [Rh(Cy2P(CH2)3PCy2)][COA⊂BArF4], in which the metal center instead forms two intramolecular agostic η1 Rh···H–C interactions with the phosphine cyclohexyl groups. CH2Cl2 adducts formed by displacement of the η1-alkanes in solution (n = 5; L = NBA, COA), [RhH(Cy2P(CH2)2(CH)(CH2)2PCy2)(κ1-ClCH2Cl)][BArF4], are characterized crystallographically. Analyses via periodic DFT, QTAIM, NBO, and NCI calculations, alongside variable temperature solid-state NMR spectroscopy, provide snapshots marking the onset of Rh···alkane interactions along a C–H activation trajectory. These are negligible in [Rh(Cy2P(CH2)3PCy2)][COA⊂BArF4]; in [RhH(Cy2P(CH2)2(CH)(CH2)2PCy2)(η1-COA)][BArF4], σC–H → Rh σ-donation is supported by Rh → σ*C–H “pregostic” donation, and in [Rh(Cy2P(CH2)nPCy2)(η2η2-NBA)][BArF4] (n = 2–4), σ-donation dominates, supported by classical Rh(dπ) → σ*C–H π-back-donation. Dispersive interactions with the [BArF4]− anions and Cy substituents further stabilize the alkanes within the binding pocket." @default.
• W2896058167 created "2018-10-26" @default.
• W2896058167 creator A5003107313 @default.
• W2896058167 creator A5014634951 @default.
• W2896058167 creator A5025784191 @default.
• W2896058167 creator A5031577471 @default.
• W2896058167 creator A5038632115 @default.
• W2896058167 creator A5043306923 @default.
• W2896058167 creator A5050128351 @default.
• W2896058167 creator A5050160701 @default.
• W2896058167 creator A5059603415 @default.
• W2896058167 creator A5087642038 @default.
• W2896058167 date "2018-10-10" @default.
• W2896058167 modified "2023-10-14" @default.
• W2896058167 title "Modulation of σ-Alkane Interactions in [Rh(L₂)(alkane)]⁺ Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to η²,η²-σ-Alkane Rh(I), η¹-σ-Alkane Rh(III) Complexes, and Alkane Encapsulation" @default.
• W2896058167 cites W1877772255 @default.
• W2896058167 cites W1963761806 @default.
• W2896058167 cites W1964821644 @default.
• W2896058167 cites W1966949133 @default.
• W2896058167 cites W1973013914 @default.
• W2896058167 cites W1975959062 @default.
• W2896058167 cites W1982603256 @default.
• W2896058167 cites W1986515064 @default.
• W2896058167 cites W1989803389 @default.
• W2896058167 cites W1992535972 @default.
• W2896058167 cites W1994562101 @default.
• W2896058167 cites W1996404107 @default.
• W2896058167 cites W2005011184 @default.
• W2896058167 cites W2011573181 @default.
• W2896058167 cites W2013094776 @default.
• W2896058167 cites W2015109253 @default.
• W2896058167 cites W2021200484 @default.
• W2896058167 cites W2022403881 @default.
• W2896058167 cites W2036714532 @default.
• W2896058167 cites W2040122596 @default.
• W2896058167 cites W2040530319 @default.
• W2896058167 cites W2041086195 @default.
• W2896058167 cites W2043973654 @default.
• W2896058167 cites W2044071493 @default.
• W2896058167 cites W2049477866 @default.
• W2896058167 cites W2060962827 @default.
• W2896058167 cites W2074664376 @default.
• W2896058167 cites W2074863525 @default.
• W2896058167 cites W2075682704 @default.
• W2896058167 cites W2081224247 @default.
• W2896058167 cites W2084455356 @default.
• W2896058167 cites W2088863825 @default.
• W2896058167 cites W2092019027 @default.
• W2896058167 cites W2093088840 @default.
• W2896058167 cites W2112516896 @default.
• W2896058167 cites W2113685445 @default.
• W2896058167 cites W2123257409 @default.
• W2896058167 cites W2141725143 @default.
• W2896058167 cites W2146929798 @default.
• W2896058167 cites W2152782786 @default.
• W2896058167 cites W2155678824 @default.
• W2896058167 cites W2158573995 @default.
• W2896058167 cites W2159878637 @default.
• W2896058167 cites W2169986863 @default.
• W2896058167 cites W2194571075 @default.
• W2896058167 cites W2211144432 @default.
• W2896058167 cites W2224728609 @default.
• W2896058167 cites W2315137491 @default.
• W2896058167 cites W2317186746 @default.
• W2896058167 cites W2319755249 @default.
• W2896058167 cites W2319817746 @default.
• W2896058167 cites W2321983796 @default.
• W2896058167 cites W2323416647 @default.
• W2896058167 cites W2323613375 @default.
• W2896058167 cites W2323968932 @default.
• W2896058167 cites W2327489856 @default.
• W2896058167 cites W2330058553 @default.
• W2896058167 cites W2333901610 @default.
• W2896058167 cites W2338552273 @default.
• W2896058167 cites W2472471549 @default.
• W2896058167 cites W2519659119 @default.
• W2896058167 cites W2522118572 @default.
• W2896058167 cites W2559101029 @default.
• W2896058167 cites W2580011036 @default.
• W2896058167 cites W2591006714 @default.
• W2896058167 cites W2591215381 @default.
• W2896058167 cites W2601224882 @default.
• W2896058167 cites W2606147374 @default.
• W2896058167 cites W2626528367 @default.
• W2896058167 cites W2726493813 @default.
• W2896058167 cites W2748054623 @default.
• W2896058167 cites W2777651827 @default.
• W2896058167 cites W2778644647 @default.
• W2896058167 cites W2784334464 @default.
• W2896058167 cites W2791612975 @default.
• W2896058167 cites W2805423929 @default.
• W2896058167 cites W2805492381 @default.
• W2896058167 cites W2949260953 @default.
• W2896058167 cites W4210333567 @default.
• W2896058167 cites W4211167782 @default.
• W2896058167 cites W4231822216 @default.
• W2896058167 cites W4234957434 @default.
• W2896058167 cites W4242347576 @default.

• next