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- W56663535 abstract "ion. 2.3. Concluding Remarks In this chapter, the reaction of W(CH2SiMe3)3(≡CSiMe3) (1) with DMPE (DMPE = Me2PCH2CH2PMe2) gives an adduct W(CH2SiMe3)3(≡CSiMe3)(DMPEP) (4a). 4a undergoes a rarely observed reversible transformation to its bisalkylidene tautomer W(CH2SiMe3)2(=CHSiMe3)2(DMPE-P) (4b) through α–H migration. The DMPE ligands in both 4a and 4b contain a dangling P atom (P). Thermodynamic and kinetic studies of the 4a o 4b exchange show that it is slightly endothermic with ΔH° = 5.1(1.1) kcal/mol and ΔS° = 24(4) eu; ΔH1 = 4.0(0.9) kcal/mol, ΔS1 = –51(2) eu for the 4a → 4b forward reaction; ΔH-1 = 2.0(0.8) kcal/mol, ΔS-1 = –76(1) eu for the 4b → 4a reverse reaction. Activation entropies are the major contributors to the activation barriers of the exchange: ΔG1278K = 21.7(1.5) kcal/mol and ΔG-1278K = 23.1(1.1) kcal/mol. The 4a o 4b exchange at 283 K is faster than that of the previously reported PMe3 analogs W(CH2SiMe3)3(≡CSiMe3)(PMe3) (2a) o W(CH2SiMe3)2(=CHSiMe3)2(PMe3) (2b). The 4a o 4b mixture undergoes an α–H abstraction, yielding alkyl alkylidene alkylidyne complexes W(CH2SiMe3)(=CHSiMe3)(≡CSiMe3)(DMPE) (syn: 7a; anti:" @default.
- W56663535 created "2016-06-24" @default.
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- W56663535 date "2009-01-01" @default.
- W56663535 modified "2023-09-25" @default.
- W56663535 title "Studies of Tungsten Alkyl Alkylidyne Compounds and Iron Porphyrin Derivatives" @default.
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