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• W3122371108 endingPage "121708" @default.
• W3122371108 startingPage "121708" @default.
• W3122371108 abstract "The unsaturated hydride [MoWCp2(H)(μ-PCy2)(CO)2] (1) reacted rapidly with stoichiometric amounts of different isocyanides at room temperature to give two types of formimidoyl derivatives: the symmetrically bridged complexes [MoWCp2(μ-η2:η2-CHNR)(μ-PCy2)(CO)2] [R = tBu (2a), 4-C6H4OMe (2b)], and the asymmetrically bridged complex [MoWCp2(μ-1κC:2κN-HCNR)(μ-PCy2)(CO)2] [R = Xyl (3)], with the latter compound undergoing slow rearrangement above 293 K to give the aminocarbyne isomer [MoWCp2{μ-CNH(Xyl)}(μ-PCy2)(CO)2] (4). The reaction of 1 with excess CNtBu led to the double addition product [MoWCp2(μ-H)(μ-PCy2)(1κ-CNtBu)(2κ-CNtBu)(1κ-CO)(2κ-CO)] (5), whereas the reaction with excess CN(4-C6H4OMe) at room temperature gave a mixture of two complexes having 5-electron donor aminocarbene-iminoacyl ligands: [MoWCp2(μ-1η2:2κC,κC´-HCN(4-C6H4OMe)C{N(4-C6H4OMe)})(μ-PCy2)(CO)2] (6) and [MoWCp2(μ-1κC,κC´:2η2-HCN(4-C6H4OMe)C{N(4-C6H4OMe)})(μ-PCy2){2κ-CN(4-C6H4OMe)}(1κ-CO)] (7) following from formimidoyl-isocyanide coupling. The title hydride reacted with N2CH(SiMe3) to give the addition product [MoWCp2(1κ-H)(μ-PCy2)(2κ-CO)2{1κ-N2CH(SiMe3)}] (8c), in which the coordinated diazoalkane acts formally as an imido-like four-electron donor group. Reaction with N2CPh2 led instead to a mixture of four products derived from the addition of either one molecule of diazoalkane: [MoWCp2(1κ-H)(μ-PCy2)(2κ-CO)2(1κ-N2CPh2)] (8d-W) and [MoWCp2(2κ-H)(μ-PCy2)(1κ-CO)2(2κ-N2CPh2)] (8d-Mo), or two molecules of the reagent: [MoWCp2(2κ-H)(μ-PCy2)(2κ-CO)2(1κ-N2CPh2)2] (9d-Mo) and [MoWCp2(1κ-H)(μ-PCy2)(1κ-CO)2(2κ-N2CPh2)2] (9d-W). These latter products lack of a metal−metal bond due to a dissimilar electron donation from the diazoalkane ligands, which act as 2- and 4-electron donors, respectively. Reaction of 1 with excess (p-tol)C(O)H (p-tol = 4-C6H4Me) in refluxing toluene gave the oxoacyl complex [MoWCp2{μ-1κC:2η2-C(O)CH2(p-tol)}(1κ-O)(μ-PCy2)(2κ-CO)] (10) as the unique product, following from C–O bond cleavage of the incoming reagent. Finally, compound 1 reacted with HC2(p-tol) at room temperature to give a mixture of the α-substituted alkenyls trans-[MoWCp2{μ-κ:η2-C(p-tol)CH2}(μ-PCy2)(CO)2] (trans-11) and cis-[MoWCp2{μ-1κ:2η2-C(p-tol)CH2}(μ-PCy2)(CO)2] (cis-11) in a ratio ca. 7/1, whereas the reaction in refluxing toluene led to mixtures of the β-substituted alkenyls trans-[MoWCp2{μ-1κ:2η2-CHCH(p-tol)}(μ-PCy2)(CO)2] (trans-12) and cis-[MoWCp2{μ-κ:η2-CHCH(p-tol)}(μ-PCy2)(CO)2] (cis-12) in a ratio ca. 10/1, with the former α-substituted complexes fully rearranging into the β-substituted alkenyls rapidly at 363 K, as shown by independent experiments." @default.
• W3122371108 created "2021-02-01" @default.
• W3122371108 creator A5030874852 @default.
• W3122371108 creator A5058269417 @default.
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• W3122371108 creator A5084407205 @default.
• W3122371108 creator A5090547405 @default.
• W3122371108 date "2021-03-01" @default.
• W3122371108 modified "2023-10-17" @default.
• W3122371108 title "A glimpse into the chemical reactivity of the unsaturated hydride [MoWCp2(H)(μ-PCy2)(CO)2]" @default.
• W3122371108 cites W1591489016 @default.
• W3122371108 cites W1966182479 @default.
• W3122371108 cites W1970564066 @default.
• W3122371108 cites W1971285225 @default.
• W3122371108 cites W1971506855 @default.
• W3122371108 cites W1972980505 @default.
• W3122371108 cites W1973458202 @default.
• W3122371108 cites W1974092755 @default.
• W3122371108 cites W1974742672 @default.
• W3122371108 cites W1975074586 @default.
• W3122371108 cites W1975170784 @default.
• W3122371108 cites W1980853762 @default.
• W3122371108 cites W1981745234 @default.
• W3122371108 cites W1982098588 @default.
• W3122371108 cites W1986546695 @default.
• W3122371108 cites W1988484491 @default.
• W3122371108 cites W1989655518 @default.
• W3122371108 cites W1992275761 @default.
• W3122371108 cites W1995993593 @default.
• W3122371108 cites W2002982017 @default.
• W3122371108 cites W2003338214 @default.
• W3122371108 cites W2006528848 @default.
• W3122371108 cites W2009436238 @default.
• W3122371108 cites W2010435143 @default.
• W3122371108 cites W2011951650 @default.
• W3122371108 cites W2013931737 @default.
• W3122371108 cites W2019388050 @default.
• W3122371108 cites W2023271753 @default.
• W3122371108 cites W2036062080 @default.
• W3122371108 cites W2038909140 @default.
• W3122371108 cites W2040282909 @default.
• W3122371108 cites W2041852689 @default.
• W3122371108 cites W2042203470 @default.
• W3122371108 cites W2052573265 @default.
• W3122371108 cites W2055779156 @default.
• W3122371108 cites W2058069477 @default.
• W3122371108 cites W2058867126 @default.
• W3122371108 cites W2063334178 @default.
• W3122371108 cites W2066727234 @default.
• W3122371108 cites W2067276739 @default.
• W3122371108 cites W2067601423 @default.
• W3122371108 cites W2067795148 @default.
• W3122371108 cites W2068969687 @default.
• W3122371108 cites W2069348739 @default.
• W3122371108 cites W2077379725 @default.
• W3122371108 cites W2091331971 @default.
• W3122371108 cites W2094642658 @default.
• W3122371108 cites W2110397077 @default.
• W3122371108 cites W2120087907 @default.
• W3122371108 cites W2120532777 @default.
• W3122371108 cites W2130086905 @default.
• W3122371108 cites W2131350133 @default.
• W3122371108 cites W2131352956 @default.
• W3122371108 cites W2139962349 @default.
• W3122371108 cites W2143981217 @default.
• W3122371108 cites W2145024056 @default.
• W3122371108 cites W2155428573 @default.
• W3122371108 cites W2163003488 @default.
• W3122371108 cites W2167601354 @default.
• W3122371108 cites W2172451747 @default.
• W3122371108 cites W2279861329 @default.
• W3122371108 cites W2280849059 @default.
• W3122371108 cites W2313732901 @default.
• W3122371108 cites W2320520552 @default.
• W3122371108 cites W2323726729 @default.
• W3122371108 cites W2333779536 @default.
• W3122371108 cites W2460160653 @default.
• W3122371108 cites W2510805070 @default.
• W3122371108 cites W2742638984 @default.
• W3122371108 cites W2793815228 @default.
• W3122371108 cites W2799930015 @default.
• W3122371108 cites W2800314964 @default.
• W3122371108 cites W2900386486 @default.
• W3122371108 cites W2942713284 @default.
• W3122371108 cites W2950016078 @default.
• W3122371108 cites W2951278022 @default.
• W3122371108 cites W2952013501 @default.
• W3122371108 cites W2952068096 @default.
• W3122371108 cites W3004436494 @default.
• W3122371108 cites W3005066955 @default.
• W3122371108 cites W3092479292 @default.
• W3122371108 cites W4230123174 @default.
• W3122371108 cites W4293208197 @default.
• W3122371108 doi "https://doi.org/10.1016/j.jorganchem.2021.121708" @default.
• W3122371108 hasPublicationYear "2021" @default.
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