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Title: Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands

Abstract

Here, the synthesis and characterization of new 1,2,4-triazolyl and 4-nitro-pyrazolyl substituted tetrazine ligands has been achieved. The strongly electron deficient 1,2,4-triazolyl substituted ligands did not coordinate Fe(II) metal centers, while the mildly electron deficient 4-nitro-pyrazolyl substituted ligands did coordinate Fe(II) metal centers in a 2:1 ratio of ligand to metal. The thermal stability and mechanical sensitivity characteristics of the complexes are similar to the conventional explosive pentaerythritol tetranitrate. The complexes had strong absorption in the visible region of the spectrum that extended into the near-infrared. In spite of having improved oxygen balances, increased mechanical sensitivity, and similar absorption of NIR light to recently reported Fe(II) tetrazine complexes, these newly synthesized explosives were more difficult to initiate with Nd:YAG pulsed laser light. More specifically, the complexes required lower densities (0.9 g/cm 3) to initiate at the same threshold utilized to initiate previous materials at higher densities (1.05 g/cm 3).

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1351988
Report Number(s):
LA-UR-16-29289
Journal ID: ISSN 0020-1669
Grant/Contract Number:
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 4; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Myers, Thomas Winfield, Brown, Kathryn Elizabeth, Chavez, David E., Scharff, Robert Jason, and Veauthier, Jacqueline Marie. Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.6b02998.
Myers, Thomas Winfield, Brown, Kathryn Elizabeth, Chavez, David E., Scharff, Robert Jason, & Veauthier, Jacqueline Marie. Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands. United States. doi:10.1021/acs.inorgchem.6b02998.
Myers, Thomas Winfield, Brown, Kathryn Elizabeth, Chavez, David E., Scharff, Robert Jason, and Veauthier, Jacqueline Marie. Wed . "Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands". United States. doi:10.1021/acs.inorgchem.6b02998. https://www.osti.gov/servlets/purl/1351988.
@article{osti_1351988,
title = {Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands},
author = {Myers, Thomas Winfield and Brown, Kathryn Elizabeth and Chavez, David E. and Scharff, Robert Jason and Veauthier, Jacqueline Marie},
abstractNote = {Here, the synthesis and characterization of new 1,2,4-triazolyl and 4-nitro-pyrazolyl substituted tetrazine ligands has been achieved. The strongly electron deficient 1,2,4-triazolyl substituted ligands did not coordinate Fe(II) metal centers, while the mildly electron deficient 4-nitro-pyrazolyl substituted ligands did coordinate Fe(II) metal centers in a 2:1 ratio of ligand to metal. The thermal stability and mechanical sensitivity characteristics of the complexes are similar to the conventional explosive pentaerythritol tetranitrate. The complexes had strong absorption in the visible region of the spectrum that extended into the near-infrared. In spite of having improved oxygen balances, increased mechanical sensitivity, and similar absorption of NIR light to recently reported Fe(II) tetrazine complexes, these newly synthesized explosives were more difficult to initiate with Nd:YAG pulsed laser light. More specifically, the complexes required lower densities (0.9 g/cm3) to initiate at the same threshold utilized to initiate previous materials at higher densities (1.05 g/cm3).},
doi = {10.1021/acs.inorgchem.6b02998},
journal = {Inorganic Chemistry},
number = 4,
volume = 56,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2017},
month = {Wed Feb 01 00:00:00 EST 2017}
}

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  • The new technetium(V)sulfido complexes [TcS(edt)[sub 2]][sup [minus]] (1) and [TcSCl[sub 2](HB(pz)[sub 3])] (3) have been prepared and characterized. These species constitute the first examples of technetium complexes containing a terminal Tc[double bond]S bond. Complex 1 was obtained from [TcCl[sub 6]][sup 2[minus]] by reaction with ethane-1,2-dithiol (H[sub 2]edt), while 3 was formed from [TcOCl[sub 2](HB(pz)[sub 3])] by atom transfer from B[sub 2]S[sub 3]. The rhenium analog of complex 3, [ReSCl[sub 2](HB(pz)[sub 3])] (4), has been also prepared. In the synthesis of 1, the dimeric Tc(IV) complex [Tc[sub 2](edt)[sub 2](e[double bond]dt)[sub 2]] (2) (e[double bond]dt = ethene-1,2-dithiolato) was isolated by precipitation. 2more » represents the first example of a technetium complex containing two terminal dithiolene and two bridged dithiolato ligands. The conversion of ethane-1,2-dithiolato to ethene-1,2-dithiolato in the reaction of preparation of 1 and 2 seems to play a key role in the formation of the [Tc[double bond]S][sup 3+] core. The X-ray crystal structure of complex 2 showed the Tc atom in a trigonal prismatic array. 2 crystallizes in the triclinic space group P[bar 1]. The reactions of various monothiols and dithiols with [MCl[sub 6]][sup 2[minus]] and [MOCl[sub 2](HB(pz)[sub 3])] (M = Tc, Re) are also discussed. The X-ray crystal structure of one product of these reactions, namely the complex [ReO(edt)(HB(pz)[sub 3])] (5), has been determined. 5 was monomeric with the Re atom in a distorted octahedral environment. It crystallizes in the monoclinic space group P2[sub 1]/c. 31 refs., 3 figs., 5 tabs.« less
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