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Molecular titanium nitrides: nucleophiles unleashed.

ABSTRACT: In this contribution we present reactivity studies of a rare example of a titanium salt, in the form of [μ₂-K(OEt₂)]₂[(PN)₂Ti[triple bond, length as m-dash]N]₂ (1) (PN^- = N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) to produce a series of imide moieties including rare examples such as methylimido, borylimido, phosphonylimido, and a parent imido. For the latter, using various weak acids allowed us to narrow the pK _a range of the NH group in (PN)₂Ti[triple bond, length as m-dash]NH to be between 26-36. Complex 1 could be produced by a reductively promoted elimination of N₂ from the azide precursor (PN)₂TiN₃, whereas reductive splitting of N₂ could not be achieved using the complex (PN)₂Ti[double bond, length as m-dash]N[double bond, length as m-dash]N[double bond, length as m-dash]Ti(PN)₂ (2) and a strong reductant. Complete N-atom transfer reactions could also be observed when 1 was treated with ClC(O)^tBu and OCCPh₂ to form NC^tBu and KNCCPh₂, respectively, along with the terminal oxo complex (PN)₂Ti[triple bond, length as m-dash]O, which was also characterized. A combination of solid state ¹⁵N NMR (MAS) and theoretical studies allowed us to understand the shielding effect of the counter cation in dimer 1, the monomer [K(18-crown-6)][(PN)₂Ti[triple bond, length as m-dash]N], and the discrete salt [K(2,2,2-Kryptofix)][(PN)₂Ti[triple bond, length as m-dash]N] as well as the origin of the highly downfield ¹⁵N NMR resonance when shifting from dimer to monomer to a terminal nitride (discrete salt). The upfield shift of ¹⁵N_nitride resonance in the ¹⁵N NMR spectrum was found to be linked to the K⁺ induced electronic structural change of the titanium-nitride functionality by using a combination of MO analysis and quantum chemical analysis of the corresponding shielding tensors.

SUBMITTER: Grant LN

PROVIDER: S-EPMC5369542 | biostudies-literature | 2017 Feb

REPOSITORIES: biostudies-literature

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Molecular titanium nitrides: nucleophiles unleashed.

Grant Lauren N LN Pinter Balazs B Kurogi Takashi T Carroll Maria E ME Wu Gang G Manor Brian C BC Carroll Patrick J PJ Mindiola Daniel J DJ

Chemical science 20160922 2

In this contribution we present reactivity studies of a rare example of a titanium salt, in the form of [μ2-K(OEt2)]2[(PN)2Ti[triple bond, length as m-dash]N]2 (1) (PN- = N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) to produce a series of imide moieties including rare examples such as methylimido, borylimido, phosphonylimido, and a parent imido. For the latter, using various weak acids allowed ...[more]

PMID: 28451262

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Project description:Elemental profiling of fungal species as a phenotyping tool is an understudied topic and is typically performed to examine plant tissue or non-biological materials. Traditional analytical techniques such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) have been used to identify elemental profiles of fungi; however, these techniques can be cumbersome due to the difficulty of preparing samples. Additionally, the instruments used for these techniques can be expensive to procure and operate. Laser-induced breakdown spectroscopy (LIBS) is an alternative elemental analytical technique-one that is sensitive across the periodic table, easy to use on various sample types, and is cost-effective in both procurement and operation. LIBS has not been used on axenic filamentous fungal isolates grown in substrate media. In this work, as a proof of concept, we used LIBS on two genetically distinct fungal species grown on a nutrient-rich and nutrient-poor substrate media to determine whether robust elemental profiles can be detected and whether differences between the fungal isolates can be identified. Our results demonstrate a distinct correlation between fungal species and their elemental profile, regardless of the substrate media, as the same strains shared a similar uptake of carbon, zinc, phosphorus, manganese, and magnesium, which could play a vital role in their survival and propagation. Independently, each fungal species exhibited a unique elemental profile. This work demonstrates a unique and valuable approach to rapidly phenotype fungi through optical spectroscopy, and this approach can be critical in understanding these fungi's behavior and interactions with the environment.ImportanceHistorically, ionomics, the elemental profiling of an organism or materials, has been used to understand the elemental composition in waste materials to identify and recycle heavy metals or rare earth elements, identify the soil composition in space exploration on the moon or Mars, or understand human disorders or disease. To our knowledge, ionomic profiling of microbes, particularly fungi, has not been investigated to answer applied and fundamental biological questions. The reason is that current ionomic analytical techniques can be laborious in sample preparation, fail to measure all potential elements accurately, are cost-prohibitive, or provide inconsistent results across replications. In our previous efforts, we explored whether laser-induced breakdown spectroscopy (LIBS) could be used in determining the elemental profiles of poplar tissue, which was successful. In this proof-of-concept endeavor, we undertook a transdisciplinary effort between applied and fundamental mycology and elemental analytical techniques to address the biological question of how LIBS can used for fungi grown axenically in a nutrient-rich and nutrient-poor environment.

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Molecular titanium nitrides: nucleophiles unleashed.

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Molecular titanium nitrides: nucleophiles unleashed.

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