Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

No right to sext? A critical examination of media and legal debates about teenage girls' sexual agency in the digital age

Advances in digital photography and distribution technologies enable many people to produce and distribute images of their sex acts. When teenagers do this, the photos and videos they create can be legally classified as child pornography since the law makes no exception for youth who create sexually explicit images of themselves. The dominant discussions about teenage girls producing sexually explicit media (including sexting) are profoundly unproductive: (1) they blame teenage girls for creating private images that another person later maliciously distributed and (2) they fail to respect—or even discuss—teenagers’ rights to freedom of expression. Cell phones and the internet make producing and distributing images extremely easy, which provide widely accessible venues for both consensual sexual expression between partners and for sexual harassment. Dominant understandings view sexting as a troubling teenage trend created through the combination of camera phones and adolescent hormones and impulsivity, but this view often conflates consensual sexting between partners with the malicious distribution of a person’s private image as essentially equivalent behaviors. In this project, I ask: What is the role of assumptions about teen girls’ sexual agency in these problematic understandings of sexting that blame victims and deny teenagers’ rights? In contrast to the popular media panic about online predators and the familiar accusation that youth are wasting their leisure time by using digital media, some people champion the internet as a democratic space that offers young people the opportunity to explore identities and develop social and communication skills. Yet, when teen girls’ sexuality enters this conversation, all this debate and discussion narrows to a problematic consensus. The optimists about adolescents and technology fall silent, and the argument that media production is inherently empowering for girls does not seem to apply to a girl who produces a sexually explicit image of herself. Instead, feminist, popular, and legal commentaries assert that she is necessarily a victim: of a “sexualized” mass media, pressure from her male peers, digital technology, her brain structures or hormones, or her own low self-esteem and misplaced desire for attention. Why and how are teenage girls’ sexual choices produced as evidence of their failure or success in achieving Western liberal ideals of self-esteem, resistance, and agency? Since mass media and policy reactions to sexting have so far been overwhelmingly sexist and counter-productive, it is crucial to interrogate the concepts and assumptions that characterize mainstream understandings of sexting. I argue that the common sense that is co-produced by law and mass media underlies the problematic legal and policy responses to sexting. Analyzing a range of nonfiction texts including newspaper articles, talk shows, press releases, public service announcements, websites, legislative debates, and legal documents, I investigate gendered, racialized, age-based, and technologically determinist common sense assumptions about teenage girls’ sexual agency. I examine the consensus and continuities that exist between news, nonfiction mass media, policy, institutions, and law, and describe the limits of their debates. I find that this early 21st century post-feminist girl-power moment not only demands that girls live up to gendered sexual ideals but also insists that actively choosing to follow these norms is the only way to exercise sexual agency. This is the first study to date examining the relationship of conventional wisdom about digital media and teenage girls’ sexuality to both policy and mass media.