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• W2022503903 endingPage "4039" @default.
• W2022503903 startingPage "4026" @default.
• W2022503903 abstract "The addition of acids to ferrous dinitrogen complexes [FeX(N2)(P(Et)N(Me)P(Et))(dmpm)](+) (X = H, Cl, or Br; P(Et)N(Me)P(Et) = Et2PCH2N(Me)CH2PEt2; and dmpm = Me2PCH2PMe2) gives protonation at the pendent amine of the diphosphine ligand rather than at the dinitrogen ligand. This protonation increased the νN2 band of the complex by 25 cm(-1) and shifted the Fe(II/I) couple by 0.33 V to a more positive potential. A similar IR shift and a slightly smaller shift of the Fe(II/I) couple (0.23 V) was observed for the related carbonyl complex [FeH(CO)(P(Et)N(Me)P(Et))(dmpm)](+). [FeH(P(Et)N(Me)P(Et))(dmpm)](+) was found to bind N2 about three times more strongly than NH3. Computational analysis showed that coordination of N2 to Fe(II) centers increases the basicity of N2 (vs free N2) by 13 and 20 pKa units for the trans halides and hydrides, respectively. Although the iron center increases the basicity of the bound N2 ligand, the coordinated N2 is not sufficiently basic to be protonated. In the case of ferrous dinitrogen complexes containing a pendent methylamine, the amine site was determined to be the most basic site by 30 pKa units compared to the N2 ligand. The chemical reduction of these ferrous dinitrogen complexes was performed in an attempt to increase the basicity of the N2 ligand enough to promote proton transfer from the pendent amine to the N2 ligand. Instead of isolating a reduced Fe(0)-N2 complex, the reduction resulted in isolation and characterization of HFe(Et2PC(H)N(Me)CH2PEt2)(P(Et)N(Me)P(Et)), the product of oxidative addition of the methylene C-H bond of the P(Et)N(Me)P(Et) ligand to Fe." @default.
• W2022503903 created "2016-06-24" @default.
• W2022503903 creator A5022980951 @default.
• W2022503903 creator A5026533086 @default.
• W2022503903 creator A5041718010 @default.
• W2022503903 creator A5061767165 @default.
• W2022503903 creator A5069947980 @default.
• W2022503903 creator A5074246530 @default.
• W2022503903 creator A5088556197 @default.
• W2022503903 date "2013-03-18" @default.
• W2022503903 modified "2023-09-27" @default.
• W2022503903 title "Protonation of Ferrous Dinitrogen Complexes Containing a Diphosphine Ligand with a Pendent Amine" @default.
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