The five-coordinate compound, Salen((t)Bu)Al(Ac), prepared in situ from Salen((t)Bu)AlBr and NH4Ac, forms Lewis acid-base adducts in aqueous solution with the G-type nerve agents, Sarin and Soman, and the VX hydrolysis product, ethylmethylphosphonate (EMPA). The resulting compounds, [Salen((t)Bu)Al(NA)](+)[Ac] (-) (with NA = Sarin, Soman, and EMPA) are sufficiently stable to be identified by ESI-MS. Molecular ion peaks were detected for every compound with little or no fragmentation. The distinctive MS signatures for the [Salen((t)Bu)Al(NA)](+) compounds provide a new technique for identifying nerve agents from aqueous solution. The energetics of the displacement of Ac(-) by the nerve agents to form [Salen((t)Bu)Al(NA)](+)[Ac](-) were determined computationally.
Group 13 chelates incorporating boron and aluminum deactivated the chemical warfare agents (CWAs) VX, sarin (GB), soman (GD), and the pesticide, diazinon, under mild conditions. The deactivation occured through elimination of alkyl bromide resulting in solid products containing a robust Al-O-P or B-O-P linkage. The Group 13 chelate deactivation methodology produces non-toxic, easily disposable solid proudcts after combination with CWAs. In previous studies the group 13 chelates were found to be active for a wide range of organophosphates, organophosphonates, and organophosphinates (OPs). Thus, the compounds could be used as a deactivating agent for a wide range of problematic compounds possessing P-O-C linkages, including, CWAs, pesticides, and plasticizers. The majority of the chelate compounds are of the general formula: LBX , L(BX2)2 and LAlX where L = an inexpensive, easily prepared Schiff base chelate and X = Cl and Br. This article will describe the range of compounds that can be used in the dealkylation reaction. The primary focus will be on chelates of the Salen class (Salen = N, N ′ -alkylene(or arylene)bis(salicylideneimine)), but a wider of range of chelates could be used for the reaction as this review will demonstrate.
Three salen aluminum bromide compounds salen( t Bu)AlBr (1) (salen = N,N′-ethylenebis(3,5-di-tertbutylsalicylideneimine)), salpen( t Bu)AlBr (2) (salpen = N,N′-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen( t Bu)-AlBr (3) (salophen = N,N′-o-phenylenenebis(3,5-di-tert-butylsalicylideneimine) were evaluated for their potential use as dealkylation agents with a series of organophosphates. These reactions led to the aluminum phosphate compounds containing six-coordinate aluminum centers and hydrolytically stable P−O−C bonds:] 2 , 9 = (salen( t Bu)AlO) 3 PO, 10 = (salpen( t Bu)AlO) 3 PO, 11 = (salophen( t Bu)AlO) 3 PO. All the compounds were characterized by 1 H, 13 C, 27 Al, and 31 P NMR, IR, and mass spectrometry. Furthermore, compounds 4−8 were structurally characterized by single-crystal X-ray diffraction. The potential hydrolysis of these compounds was modeled with 4 and demonstrated the unique stability of the final product and ease of isolation.
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