Matches in SemOpenAlex for { <https://semopenalex.org/work/W2222564956> ?p ?o ?g. }
- W2222564956 endingPage "704" @default.
- W2222564956 startingPage "693" @default.
- W2222564956 abstract "Reaction of Cp*(Me3P)2OsCH2SiMe3 (1, Cp* = C5Me5) with an excess of iPr2Si(H)Cl afforded Cp*(Me3P)2OsSiiPr2Cl (2) in good yield, without the formation of Os(IV) products. Treatment of 2 with Me3SiOTf (OTf = triflate, OSO2CF3) afforded the corresponding triflatosilyl complex Cp*(Me3P)2OsSiiPr2OTf (3), which appears to possess substantial silylene character, as determined by structural and spectroscopic measurements. The synthetic route to these complexes is analogous to that employed for the previously reported dimethylsilyl compounds Cp*(Me3P)2OsSiMe2X (X = Cl (4), OTf (5)). Complexes 2−5 were converted to the corresponding base-free silylene complexes [Cp*(Me3P)2OsSiR2][B(C6F5)4] (R = Me (6), iPr (7)) by anion metathesis with Li[B(C6F5)4]·3Et2O. Both 6 and 7 were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The silylene complexes feature a trigonal planar environment for silicon, short Os−Si contacts (2.257(7) Å for 6, 2.263(1) Å for 7), and 29Si NMR resonances that are shifted to very low field (350 ppm for 6; 363 ppm for 7). The spectroscopic and structural differences between these silylene complexes and their precursors are discussed. While stable in fluorobenzene, 6 and 7 are rapidly oxidized by chlorocarbons via a radical pathway to form cationic Os(III) chlorosilyl species. Reactions of 7 with oxygen atom sources such as N2O and 2-picoline N-oxide afforded the N2-bridged diosmium complex [Cp*(Me3P)2Os−NN−Os(PMe3)2Cp*][B(C6F5)4]2 (8) and the cyclic siloxane (OSiiPr2)3. Reaction of 7 with elemental sulfur provided the turquoise, S2-bridged diosmium complex [Cp*(Me3P)2Os−S−S−Os(PMe3)2Cp*][B(C6F5)4]2 (9) and unidentified silicon-containing products." @default.
- W2222564956 created "2016-06-24" @default.
- W2222564956 creator A5009920753 @default.
- W2222564956 creator A5028716817 @default.
- W2222564956 creator A5079726681 @default.
- W2222564956 date "2004-01-10" @default.
- W2222564956 modified "2023-10-16" @default.
- W2222564956 title "Synthesis, Structure, and Reactivity of Osmium Silyl and Silylene Complexes Cp*(Me<sub>3</sub>P)<sub>2</sub>OsSiR<sub>2</sub>X and [Cp*(Me<sub>3</sub>P)<sub>2</sub>OsSiR<sub>2</sub>][B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (R = Me, <sup>i</sup>Pr; X = Cl, OTf)" @default.
- W2222564956 cites W1186536418 @default.
- W2222564956 cites W1501319738 @default.
- W2222564956 cites W1524616261 @default.
- W2222564956 cites W1675074845 @default.
- W2222564956 cites W1967480115 @default.
- W2222564956 cites W1969882706 @default.
- W2222564956 cites W1971388833 @default.
- W2222564956 cites W1974736243 @default.
- W2222564956 cites W1976743814 @default.
- W2222564956 cites W1979475041 @default.
- W2222564956 cites W1979485616 @default.
- W2222564956 cites W1982679755 @default.
- W2222564956 cites W1984103125 @default.
- W2222564956 cites W1984468408 @default.
- W2222564956 cites W1987046403 @default.
- W2222564956 cites W1991477025 @default.
- W2222564956 cites W1991897387 @default.
- W2222564956 cites W1991904244 @default.
- W2222564956 cites W1993710233 @default.
- W2222564956 cites W1993985002 @default.
- W2222564956 cites W1994675565 @default.
- W2222564956 cites W1999895709 @default.
- W2222564956 cites W2002628083 @default.
- W2222564956 cites W2005213341 @default.
- W2222564956 cites W2006170491 @default.
- W2222564956 cites W2012145117 @default.
- W2222564956 cites W2013666102 @default.
- W2222564956 cites W2019683950 @default.
- W2222564956 cites W2019993905 @default.
- W2222564956 cites W2021090826 @default.
- W2222564956 cites W2021149510 @default.
- W2222564956 cites W2022704821 @default.
- W2222564956 cites W2028394109 @default.
- W2222564956 cites W2031319287 @default.
- W2222564956 cites W2032402830 @default.
- W2222564956 cites W2033985825 @default.
- W2222564956 cites W2039763015 @default.
- W2222564956 cites W2042477183 @default.
- W2222564956 cites W2043304980 @default.
- W2222564956 cites W2046061930 @default.
- W2222564956 cites W2050351026 @default.
- W2222564956 cites W2051125767 @default.
- W2222564956 cites W2058518639 @default.
- W2222564956 cites W2059530602 @default.
- W2222564956 cites W2066931009 @default.
- W2222564956 cites W2067117824 @default.
- W2222564956 cites W2067639578 @default.
- W2222564956 cites W2069959718 @default.
- W2222564956 cites W2070913983 @default.
- W2222564956 cites W2071032959 @default.
- W2222564956 cites W2073662940 @default.
- W2222564956 cites W2074489959 @default.
- W2222564956 cites W2076156846 @default.
- W2222564956 cites W2080182825 @default.
- W2222564956 cites W2088016557 @default.
- W2222564956 cites W2088700758 @default.
- W2222564956 cites W2089321325 @default.
- W2222564956 cites W2095157024 @default.
- W2222564956 cites W2123294533 @default.
- W2222564956 cites W2131837115 @default.
- W2222564956 cites W2137331997 @default.
- W2222564956 cites W2149515824 @default.
- W2222564956 cites W2153548346 @default.
- W2222564956 cites W2325394540 @default.
- W2222564956 cites W2331489161 @default.
- W2222564956 cites W2332337392 @default.
- W2222564956 cites W2949216886 @default.
- W2222564956 cites W2949473783 @default.
- W2222564956 cites W2949726525 @default.
- W2222564956 cites W2950258820 @default.
- W2222564956 cites W2950923870 @default.
- W2222564956 cites W2951130227 @default.
- W2222564956 cites W2951131476 @default.
- W2222564956 cites W2952095365 @default.
- W2222564956 cites W2952791608 @default.
- W2222564956 cites W3005152881 @default.
- W2222564956 cites W4232537155 @default.
- W2222564956 cites W4234355526 @default.
- W2222564956 cites W4248612896 @default.
- W2222564956 cites W4297212879 @default.
- W2222564956 doi "https://doi.org/10.1021/om0341808" @default.
- W2222564956 hasPublicationYear "2004" @default.
- W2222564956 type Work @default.
- W2222564956 sameAs 2222564956 @default.
- W2222564956 citedByCount "51" @default.
- W2222564956 countsByYear W22225649562012 @default.
- W2222564956 countsByYear W22225649562013 @default.
- W2222564956 countsByYear W22225649562014 @default.
- W2222564956 countsByYear W22225649562015 @default.
- W2222564956 countsByYear W22225649562016 @default.