Reactivity of [(PNP)Mn(CO)2] with Organophosphates

Brooke N Livesay; Jurgen G Schmidt; Robert F Williams; Brennan S Billow; Aaron M Tondreau

doi:10.1021/acsorginorgau.3c00003

Reactivity of [(PNP)Mn(CO)₂] with Organophosphates

ACS Org Inorg Au. 2023 May 25;3(4):199-208. doi: 10.1021/acsorginorgau.3c00003. eCollection 2023 Aug 2.

Authors

Brooke N Livesay¹, Jurgen G Schmidt¹, Robert F Williams¹, Brennan S Billow¹, Aaron M Tondreau¹

Affiliation

¹ Los Alamos National Laboratory, Los Alamos, New Mexico 87544, United States.

Abstract

Organophosphorus nerve agents (OPAs) are a toxic class of synthetic compounds that cause adverse effects with many biological systems. Development of methods for environmental remediation and passivation has been ongoing for years. However, little progress has been made in therapeutic development for exposure victims. Given the postexposure behavior of OPA materials in enzymes such as acetylcholinesterase (AChE), development of electrophilic compounds as therapeutics may be more beneficial than the currently employed nucleophilic countermeasures. In this report, we present our studies with an electrophilic, 16-electron manganese complex (^iPrPNP)Mn(CO)₂ (1) and the nucleophilic hydroxide derivative (^iPrPN^HP)Mn(CO)₂(OH) (2). The reactivity of 1 with phosphorus acids and the reactivity of 2 with the P-F bond of diisopropylfluorophosphate (DIPF) were studied. The role of water in both nucleophilic and electrophilic reactivity was investigated with the use of ¹⁷O-labeled water. Promising results arising from reactions of both 1 and 2 with organophosphorus substrates are reported.