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Title: Molecular titanium nitrides: nucleophiles unleashed

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c6sc03422e· OSTI ID:1423561
 [1];  [2]; ORCiD logo [1];  [1];  [3];  [1];  [1];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
  2. Free University of Brussels (VUB) Brussels (Belgium). General Chemistry (ALGC)
  3. Queen's Univ., Kingston, ON (Canada). Dept. of Chemistry
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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$$\equiv$$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 pKa range of the NH group in (PN)2Ti$$\equiv$$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$$\equiv$$N$$\equiv$$N$$\equiv$$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 NCtBu and KNCCPh2, respectively, along with the terminal oxo complex (PN)2Ti$$\equiv$$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$$\equiv$$N], and the discrete salt [K(2,2,2-Kryptofix)][(PN)2Ti$$\equiv$$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 15Nnitride 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.

Research Organization:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Research Foundation Flanders (FWO), Brussels (Belgium)
Grant/Contract Number:
FG02-07ER15893
OSTI ID:
1423561
Journal Information:
Chemical Science, Vol. 8, Issue 2; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

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