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• W2333388762 endingPage "4396" @default.
• W2333388762 startingPage "4387" @default.
• W2333388762 abstract "Hydride abstraction from [MCpBz(CO)3H] (M = Mo, W; CpBz = C5(CH2Ph)5) using trityl cations led to [M{η5:η2-C5Bz4CH2Ph}(CO)3]BArF (BArF = B(3,5-C6H3(CF3)2)4; M = Mo (3), W (4)) or [MCpBz(CO)3(FBF3)] (M = Mo (5), W (6)) depending on the trityl counterions. The stabilization of the acidic metal centers in 3 and 4 is made through the coordination of a C═C bond of one phenyl ring, generating ansa-bridged cyclopentadienyl–phenyl carbonyl complexes. 5 and 6 are zwitterionic compounds stabilized by the coordination of the BF4 anion. An exchange process between coordinated and noncoordinated phenyl rings occurs in dichloromethane solutions of 3. VT NMR experiments gave the exchange rate at various temperatures and ΔG⧧298 = 10.1 ± 0.2 kcal mol–1. In 4 the phenyl bonding is static at room temperature, on the NMR time scale. Reactions of 3 and 4 with CO and H2O led to [MCpBz(CO)4]BArF (M = Mo (7), W (8)) and [MCpBz(CO)3(OH2)]BArF (M = Mo (11), W (12)). In CH2Cl2 solutions 3 and 4 convert slowly to 7 and 8, respectively. DFT calculations attest to the stability of 3 to H2O bonding and also show that the replacement of phenyl coordination by CO is a favorable process (ΔH = −13.8 kcal mol–1)." @default.
• W2333388762 created "2016-06-24" @default.
• W2333388762 creator A5017042384 @default.
• W2333388762 creator A5035484460 @default.
• W2333388762 creator A5039352767 @default.
• W2333388762 creator A5043885337 @default.
• W2333388762 creator A5046772276 @default.
• W2333388762 creator A5057751552 @default.
• W2333388762 date "2012-05-16" @default.
• W2333388762 modified "2023-10-17" @default.
• W2333388762 title "Hydride Abstraction from [MCp^Bz(CO)₃H] (M = Mo, W; Cp^Bz = C₅(CH₂Ph)₅): New Cationic Complexes Stabilized by η⁵:η²-C₅H₄:C₆H₅ Bonding of the Pentabenzylcyclopentadienyl Ligand" @default.
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