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• W2016092496 endingPage "4066" @default.
• W2016092496 startingPage "4057" @default.
• W2016092496 abstract "Phenylacetylene and 1,1-diphenyl-2-propyn-1-ol displace the pyridyl and ethylene ligands of OsTp{κ1-C[NC5H3Me]}(η2-CH2═CH2)(PiPr3) (1) to afford the alkynyl-vinylidene derivatives OsTp(C≡CR)(═C═CHR)(PiPr3) (Tp = hydridotris(pyrazolyl)borate; R = Ph, (2), C(OH)Ph2 (3)). Stirring of toluene solutions of 3 in the presence of neutral aluminum oxide initially produces the dehydration of the vinylidene ligand to give the alkynyl-allenylidene OsTp{C≡CC(OH)Ph2}(═C═C═CPh2)(PiPr3) (4), which subsequently undergoes a Meyer-Schuster rearrangement to yield the acyl-allenylidene OsTp{C(O)CH═CPh2}(═C═C═CPh2)(PiPr3) (5). In toluene, at 60 °C, the B–H bond of the Tp ligand of 5 abstracts the allene from the osmium coordination sphere by means of a 1,1-hydroboration of the Os–Cα double bond. As a result, the acyl decarbonylation takes place to form Os(Ph2C═C═CHTp)(CH═CPh2)(CO)(PiPr3) (6). In acetonitrile at 60 °C, the allene tautomerizes into the alkyne to afford Os(Ph2HCC≡CTp)(CH═CPh2)(CO)(PiPr3) (7). The abstraction modifies the reactivity of the system toward HBF4. Thus, while the protonation of 5 leads to the alkylidyne [OsTp{C(O)CH═CPh2}(≡CCH═CPh2)(PiPr3)]BF4 (8), the protonation of 6 and 7 gives the alkylidenes [Os(Ph2C═C═CHTp)(═CHCHPh2)(CO)(PiPr3)]BF4 (9) and [Os(Ph2HCC≡CTp)(═CHCHPh2)(CO)(PiPr3)]BF4 (10). Both 9 and 10 are unstable in solution. In dichloromethane, at room temperature, they evolve into the corresponding olefin derivatives [Os(Ph2C═C═CHTp)(η2-CH2═CPh2)(CO)(PiPr3)]BF4 (11) and [Os(Ph2HCC≡CTp)(η2-CH2═CPh2)(CO)(PiPr3)]BF4 (12) by means of a Cβ,Cα-hydrogen shift on the alkylidene ligand." @default.
• W2016092496 created "2016-06-24" @default.
• W2016092496 creator A5046775890 @default.
• W2016092496 creator A5052189393 @default.
• W2016092496 creator A5067242867 @default.
• W2016092496 creator A5090236062 @default.
• W2016092496 date "2014-07-22" @default.
• W2016092496 modified "2023-09-30" @default.
• W2016092496 title "Osmium-Acyl Decarbonylation Promoted by Tp-Mediated Allenylidene Abstraction: A New Role of the Tp Ligand" @default.
• W2016092496 cites W1040633427 @default.
• W2016092496 cites W1965856002 @default.
• W2016092496 cites W1966494043 @default.
• W2016092496 cites W1967628397 @default.
• W2016092496 cites W1968218061 @default.
• W2016092496 cites W1968982534 @default.
• W2016092496 cites W1969859091 @default.
• W2016092496 cites W1972880208 @default.
• W2016092496 cites W1976410107 @default.
• W2016092496 cites W1977055582 @default.
• W2016092496 cites W1978278269 @default.
• W2016092496 cites W1979030425 @default.
• W2016092496 cites W1981116754 @default.
• W2016092496 cites W1981759268 @default.
• W2016092496 cites W1988055666 @default.
• W2016092496 cites W1988512421 @default.
• W2016092496 cites W1988917889 @default.
• W2016092496 cites W1989811643 @default.
• W2016092496 cites W1995546051 @default.
• W2016092496 cites W1996387756 @default.
• W2016092496 cites W1996778213 @default.
• W2016092496 cites W1999687041 @default.
• W2016092496 cites W1999925174 @default.
• W2016092496 cites W2001280346 @default.
• W2016092496 cites W2002249180 @default.
• W2016092496 cites W2003734747 @default.
• W2016092496 cites W2004790325 @default.
• W2016092496 cites W2007252698 @default.
• W2016092496 cites W2008549537 @default.
• W2016092496 cites W2009236200 @default.
• W2016092496 cites W2010722944 @default.
• W2016092496 cites W2011606599 @default.
• W2016092496 cites W2012038126 @default.
• W2016092496 cites W2013695423 @default.
• W2016092496 cites W2014344559 @default.
• W2016092496 cites W2016245628 @default.
• W2016092496 cites W2018906235 @default.
• W2016092496 cites W2021497679 @default.
• W2016092496 cites W2022671939 @default.
• W2016092496 cites W2024242335 @default.
• W2016092496 cites W2024787348 @default.
• W2016092496 cites W2026917306 @default.
• W2016092496 cites W2027661260 @default.
• W2016092496 cites W2032631271 @default.
• W2016092496 cites W2036978853 @default.
• W2016092496 cites W2037497272 @default.
• W2016092496 cites W2038112971 @default.
• W2016092496 cites W2039199749 @default.
• W2016092496 cites W2039846649 @default.
• W2016092496 cites W2040622668 @default.
• W2016092496 cites W2041374232 @default.
• W2016092496 cites W2041623746 @default.
• W2016092496 cites W2042045563 @default.
• W2016092496 cites W2043038192 @default.
• W2016092496 cites W2043431742 @default.
• W2016092496 cites W2044476043 @default.
• W2016092496 cites W2046919289 @default.
• W2016092496 cites W2052831344 @default.
• W2016092496 cites W2057630589 @default.
• W2016092496 cites W2058916692 @default.
• W2016092496 cites W2059391700 @default.
• W2016092496 cites W2059736393 @default.
• W2016092496 cites W2062294290 @default.
• W2016092496 cites W2063161731 @default.
• W2016092496 cites W2065857235 @default.
• W2016092496 cites W2066098378 @default.
• W2016092496 cites W2067459347 @default.
• W2016092496 cites W2069992086 @default.
• W2016092496 cites W2072796268 @default.
• W2016092496 cites W2074487918 @default.
• W2016092496 cites W2078468757 @default.
• W2016092496 cites W2080503808 @default.
• W2016092496 cites W2080981670 @default.
• W2016092496 cites W2089328357 @default.
• W2016092496 cites W2089901760 @default.
• W2016092496 cites W2090213379 @default.
• W2016092496 cites W2091335149 @default.
• W2016092496 cites W2092235483 @default.
• W2016092496 cites W2094627514 @default.
• W2016092496 cites W2120944867 @default.
• W2016092496 cites W2130508436 @default.
• W2016092496 cites W2130872041 @default.
• W2016092496 cites W2131350133 @default.
• W2016092496 cites W2138356645 @default.
• W2016092496 cites W2144332006 @default.
• W2016092496 cites W2148623530 @default.
• W2016092496 cites W2153529625 @default.
• W2016092496 cites W2158945597 @default.
• W2016092496 cites W2159458318 @default.

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