FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2158755280> ?p ?o ?g. }

• W2158755280 endingPage "880" @default.
• W2158755280 startingPage "874" @default.
• W2158755280 abstract "Abstract Dodecamethyl‐2,3,5,6,7,8‐hexa‐sila‐lλ 3 ,4λ 3 ‐diphosphabicyclo[2.2.2]oc‐tane ( 1 ) and its arsenic analogue 2 are readily accessible in 69 and 73% yield, respectively, by the cyclocondensation reaction of 1,2‐dichloro‐1,1,2,2‐tetrame‐thyldisilane ( 5 ) with the lithium pnictides [LiEH 2 (dme)] (E = P ( 6 ), As( 7 ); dme = 1,2‐dimethoxyethane). The reactions proceed via 1,4‐diphosphaoctamethyltetrasi‐lacyclohexane ( 8 ) and its arsenic analogue 9 , respectively, which were isolated and structurally characterized by X‐ray crystallography. The molecular structures of 1 and 2 , which are isotypic, were also established by single‐crystal X‐ray analysis: they possess D 3 point symmetry with the expected Si–E bond lengths (E = P, As) but unusually long Si–Si bonds. The latter are 0.02–0.03 Å longer than those in 8 and 9 , mainly due to through‐bond interactions (TB) between donating n orbitals of the E atoms and the σ * acceptor orbitals of the Si–Si bond. The first expanded analogues of 1 , namely, 12 and 14 , with hexamethyltrisilane and dodecamethyl‐hexasilane chains bridging the two phosphorus atoms, were synthesized in a onepot cyclocondensation reaction of the corresponding 1,3‐ and 1,6‐dichloro‐oligosilanes 11 and 13 , respectively, with [LiPH 2 (dme)] 6 . Ab initio calculations on the parent compounds 1a, 12a , and the second‐row analogue 1,4‐diazabicyclo‐[2.2.2]octane ( B ) were carried out in order to analyze the different coupling constants and magnitudes of intramolecular interactions (through‐space/through‐bond coupling). TS and TB coupling in B were found to be about two times stronger than in the congener 1a , due to the compactness of the N 2 C 6 skeleton and the greater extent of s, p hybridization at nitrogen. Evidence for TB interactions in 1 was obtained by photoelectron spectroscopy and by comparison of the two first vertical ionization potentials with calculated values for 1a . The best agreement with experimental data was achieved when 1a was calculated at the MP2 level. Compound 1a preferentially adopts D 3 point symmetry; the higher‐symmetry D 3h form possesses one imaginary frequency and is slightly less stable (0.46 kcal mol −1 at HF/6–31 G * //HF/6–31 G * and 1.58 kcal mol −1 at MP2/ 6–31 G * //HF/6–31 G * level), suggesting that this structure corresponds to a transition state on the potential energy surface. The structures corresponding to the global minimum of B and 12a have D 3h and C 3h symmetry, respectively. At the HF/6–31 G * //HF/6–31 G * level the D 3h form of 12a is 17.61 kcal mol −1 less stable than the C 3h minimum." @default.
• W2158755280 created "2016-06-24" @default.
• W2158755280 creator A5020894344 @default.
• W2158755280 creator A5038251609 @default.
• W2158755280 creator A5048754315 @default.
• W2158755280 creator A5051647346 @default.
• W2158755280 creator A5061560326 @default.
• W2158755280 creator A5078732969 @default.
• W2158755280 creator A5089002767 @default.
• W2158755280 date "1997-06-01" @default.
• W2158755280 modified "2023-10-16" @default.
• W2158755280 title "Through‐Bond Interactions in Silicon–Phosphorus and Silicon–Arsenic Compounds: A Facile Synthesis of Dodecamethyl‐2,3,5,6,7,8‐hexasila‐1λ³,4λ³‐diphosphabicyclo[2.2.2]octane, Its Arsenic Analogue, and Related Compounds" @default.
• W2158755280 cites W147698448 @default.
• W2158755280 cites W1555832263 @default.
• W2158755280 cites W180160316 @default.
• W2158755280 cites W1965173894 @default.
• W2158755280 cites W1967527154 @default.
• W2158755280 cites W1971432803 @default.
• W2158755280 cites W1993383767 @default.
• W2158755280 cites W1994634720 @default.
• W2158755280 cites W1996462954 @default.
• W2158755280 cites W1997033908 @default.
• W2158755280 cites W2000554858 @default.
• W2158755280 cites W2008054272 @default.
• W2158755280 cites W2010624074 @default.
• W2158755280 cites W2014490590 @default.
• W2158755280 cites W2015353361 @default.
• W2158755280 cites W2015940987 @default.
• W2158755280 cites W2016038621 @default.
• W2158755280 cites W2016833682 @default.
• W2158755280 cites W2021650034 @default.
• W2158755280 cites W2026645699 @default.
• W2158755280 cites W2027427473 @default.
• W2158755280 cites W2033550891 @default.
• W2158755280 cites W2035086324 @default.
• W2158755280 cites W2037514168 @default.
• W2158755280 cites W2043979599 @default.
• W2158755280 cites W2056483534 @default.
• W2158755280 cites W2065118021 @default.
• W2158755280 cites W2072655805 @default.
• W2158755280 cites W2075146974 @default.
• W2158755280 cites W2075758407 @default.
• W2158755280 cites W2082190237 @default.
• W2158755280 cites W2082568879 @default.
• W2158755280 cites W2083560378 @default.
• W2158755280 cites W2085966856 @default.
• W2158755280 cites W2092345640 @default.
• W2158755280 cites W2094277417 @default.
• W2158755280 cites W2157002594 @default.
• W2158755280 cites W2326247458 @default.
• W2158755280 cites W2950969313 @default.
• W2158755280 doi "https://doi.org/10.1002/chem.19970030607" @default.
• W2158755280 hasPublicationYear "1997" @default.
• W2158755280 type Work @default.
• W2158755280 sameAs 2158755280 @default.
• W2158755280 citedByCount "17" @default.
• W2158755280 countsByYear W21587552802013 @default.
• W2158755280 crossrefType "journal-article" @default.
• W2158755280 hasAuthorship W2158755280A5020894344 @default.
• W2158755280 hasAuthorship W2158755280A5038251609 @default.
• W2158755280 hasAuthorship W2158755280A5048754315 @default.
• W2158755280 hasAuthorship W2158755280A5051647346 @default.
• W2158755280 hasAuthorship W2158755280A5061560326 @default.
• W2158755280 hasAuthorship W2158755280A5078732969 @default.
• W2158755280 hasAuthorship W2158755280A5089002767 @default.
• W2158755280 hasConcept C115624301 @default.
• W2158755280 hasConcept C121332964 @default.
• W2158755280 hasConcept C124600460 @default.
• W2158755280 hasConcept C134121241 @default.
• W2158755280 hasConcept C139358910 @default.
• W2158755280 hasConcept C147597530 @default.
• W2158755280 hasConcept C155860418 @default.
• W2158755280 hasConcept C178790620 @default.
• W2158755280 hasConcept C185592680 @default.
• W2158755280 hasConcept C191897082 @default.
• W2158755280 hasConcept C192562407 @default.
• W2158755280 hasConcept C193547582 @default.
• W2158755280 hasConcept C26873012 @default.
• W2158755280 hasConcept C2776624427 @default.
• W2158755280 hasConcept C2779892579 @default.
• W2158755280 hasConcept C32909587 @default.
• W2158755280 hasConcept C502230775 @default.
• W2158755280 hasConcept C544956773 @default.
• W2158755280 hasConcept C71240020 @default.
• W2158755280 hasConcept C75079739 @default.
• W2158755280 hasConcept C8010536 @default.
• W2158755280 hasConceptScore W2158755280C115624301 @default.
• W2158755280 hasConceptScore W2158755280C121332964 @default.
• W2158755280 hasConceptScore W2158755280C124600460 @default.
• W2158755280 hasConceptScore W2158755280C134121241 @default.
• W2158755280 hasConceptScore W2158755280C139358910 @default.
• W2158755280 hasConceptScore W2158755280C147597530 @default.
• W2158755280 hasConceptScore W2158755280C155860418 @default.
• W2158755280 hasConceptScore W2158755280C178790620 @default.
• W2158755280 hasConceptScore W2158755280C185592680 @default.
• W2158755280 hasConceptScore W2158755280C191897082 @default.
• W2158755280 hasConceptScore W2158755280C192562407 @default.
• W2158755280 hasConceptScore W2158755280C193547582 @default.

• next