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The d4/d3 redox pairs [MX(CO)(eta-RCCR)Tp?] z (z = 0 and 1): Structural consequences of electron transfer and implications for the inverse halide order
The d4 halide complexes [MX(CO)(eta-RCCR)Tp?] {X = F, Cl, Br or I; R = Me or Ph; M = Mo or W; Tp? = hydrotris(3,5- dimethylpyrazolyl)borate} undergo one-electron oxidation to the d3 monocations [MX(CO)(eta-RCCR)Tp?]+, isolable for M = W, R = Me. X-Ray structural studies on the redox pairs [WX(CO)(eta-MeCCMe)Tp?] z (X = Cl and Br, z = 0 and 1), the ESR spectra of the cations [WX(CO)(eta-RCCR)Tp?]+ (X = F, Cl, Br or I; R = Me or Ph), and DFT calculations on [WX(CO)(eta-MeCCMe)Tp?]z (X = F, Cl, Br and I; z = 0 and 1) are consistent with electron removal from a HOMO (of the d4 complexes) which is pi-antibonding with respect to the W-X bond, pi-bonding with respect to the W-C(O) bond, and delta-bonding with respect to the W-Calkyne bonds. The dependence of both oxidation potential and nu(CO) for [MX(CO)(eta-RCCR)Tp?] shows an inverse halide order which is consistent with an ionic component to the M-X bond; the small size of fluorine and its closeness to the metal centre leads to the highest energy HOMO and the lowest oxidation potential. In the cations [MX(CO)(eta-RCCR)Tp?] + electronegativity effects become more important, leading to a conventional order for Cl, Br and I. However, high M-F pi-donation is still facilitated by the short M-F distance. The Royal Society of Chemistry.
The d4/d3 redox pairs [MX(CO)(eta-RCCR)Tp?] z (z = 0 and 1): Structural consequences of electron transfer and implications for the inverse halide order
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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion