Cora E. MacBeth

Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity.

Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)(3-) = (N(o-PhNC(O)(i)Pr)2)(3-)) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3](1-). Magnetic measurements indicate [2](2-) to be an unusual high-spin Co(II)-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3](1-) to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3](1-) features a high-spin Co(II) center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2(•-) and the aminyl radical on redox non-innocent (L(•))(2-). Dianion [1](2-) shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2(-) π* orbital and an empty low-lying O2(-) π* orbital in [3](1-).

Transition Metal Complexes Supported by a Neutral Tetraamine Ligand Containing N,N-dimethylaniline Units

First-row transition metal-halide complexes of tris(2-dimethylaminophenyl)amine, L(Me), have been synthesized and characterized. X-ray crystallographic studies on [Co(L(Me))Br]BPh(4), [Ni(L(Me))Cl]BPh(4), [Fe(L(Me))Cl]BPh(4), and [Cu(L(Me))Cl]BF(4) have been performed, and in all cases the ligand produces five-coordinate complexes with distorted trigonal bipyramidal coordination geometries. Where possible, comparisons have been made to the structures of related neutral tripodal ligands. Spectroscopic and magnetic studies of these complexes are also described. The Cu(I)-carbonyl complexes [Cu(L(Me))(CO)]PF(6) and [Cu(Me(6)tren)(CO)]PF(6) (Me(6)tren = tris(N,N-dimethylaminoethyl)amine) have also been prepared. Infrared spectroscopic investigations of these carbonyl complexes confirm that L(Me) is a less electron donating ligand than Me(6)tren and indicate that L(Me) can impart a different coordination number in the solid-state.

Lanthanide(III) di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand.

Syntheses, structural, and spectroscopic characterization of multinuclear tris(amidate) lanthanide complexes is described. Addition of K3[N(o-PhNC(O)(t)Bu)3] to LnX3 (LnX3 = LaBr3, CeI3, and NdCl3) in N,N-dimethylformamide (DMF) results in the generation of dinuclear complexes, [Ln(N(o-PhNC(O)(t)Bu)3)(DMF)]2(μ-DMF) (Ln = La (1), Ce (2), Nd(3)), in good yields. Syntheses of tetranuclear complexes, [Ln(N(o-PhNC(O)(t)Bu)3)]4 (Ln = Ce (4), Nd(5)), resulted from protonolysis of Ln[N(SiMe3)2]3 (Ln = Ce, Nd) with N(o-PhNCH(O)(t)Bu)3. In the solid-state, complexes 1-5 exhibit coordination modes of the tripodal tris(amidate) ligand that are unique to the 4f elements and have not been previously observed in transition metal systems.

The “new normal”: Adapting doctoral trainee career preparation for broad career paths in science

Doctoral recipients in the biomedical sciences and STEM fields are showing increased interest in career opportunities beyond academic positions. While recent research has addressed the interests and preferences of doctoral trainees for non-academic careers, the strategies and resources that trainees use to prepare for a broad job market (non-academic) are poorly understood. The recent adaptation of the Social Cognitive Career Theory to explicitly highlight the interplay of contextual support mechanisms, individual career search efficacy, and self-adaptation of job search processes underscores the value of attention to this explicit career phase. Our research addresses the factors that affect the career search confidence and job search strategies of doctoral trainees with non-academic career interests and is based on nearly 900 respondents from an NIH-funded survey of doctoral students and postdoctoral fellows in the biomedical sciences at two U.S. universities. Using structural equation modeling, we find that trainees pursuing non-academic careers, and/or with low perceived program support for career goals, have lower career development and search process efficacy (CDSE), and receive different levels of support from their advisors/supervisors. We also find evidence of trainee adaptation driven by their career search efficacy, and not by career interests.

N-tert-Butyl-2-methyl­propanamide

The title compound, C8H17NO, crystallizes with two independent molecules in the asymmetric unit. In the crystal, intermolecular N—H⋯O hydrogen bonding is observed between neighboring molecules, forming continuous molecular chains along the c-axis direction.

Correction: The "new normal": Adapting doctoral trainee career preparation for broad career paths in science

[This corrects the article DOI: 10.1371/journal.pone.0177035.].

Erratum: N-tert-Butyl-2-methyl-propanamide. Corrigendum.

Corrigendum to Acta Cryst. (2011), E67, o2143.