Caitlin A Sengelaub

Publications (2)13.45 Total impact

• Article: A Transient Vanadium(III) Neopentylidene Complex. Redox Chemistry and Reactivity of the VCHtBu Functionality

  Uriah J. Kilgore, Caitlin A. Sengelaub, Hongjun Fan, John Tomaszewski, Jonathan A. Karty, Mu-Hyun Baik, Daniel J. Mindiola
  [show abstract] [hide abstract]
  ABSTRACT: The vanadium(III) bis(neopentyl) complex (PNP)V(CH2tBu)2 (PNP = N[4-Me-2-(PiPr2)C6H3]2−), a complex readily prepared from alkylation of (PNP)VCl2 with 2 equiv of LiCH2tBu, serves as a precursor to the transient vanadium(III) alkylidene complex “(PNP)VCHtBu”. Two-electron oxidation of the intermediate [(PNP)VCHtBu] with chalcogen sources results in formation of the vanadium(V) chalcogenide series (PNP)VCHtBu(X) (X = O, S, Se, Te). This family of chalcogenide−alkylidenes has been studied via 51V NMR spectroscopy in combination with DFT computational methods. The redox chemistry of [(PNP)VCHtBu] and the reactivity of the alkylidene ligand are explored with the substrates N3SiMe3, NCtBu, N2, and azobenzene. It was discovered that NN cleavage of the last substrate can be achieved without oxidation of the metal.
  12/2008;
• Article: A transient V(III)-alkylidene complex: oxidation chemistry including the activation of N2 to afford a highly porous honeycomb-like framework.

  Uriah J Kilgore, Caitlin A Sengelaub, Maren Pink, Alison R Fout, Daniel J Mindiola
  Angewandte Chemie International Edition 02/2008; 47(20):3769-72. · 13.45 Impact Factor