Gas Phase Reactions of Dimethoxy Phosphoryl Anion (CH3O)2PO(-).
Abstract
Dimethoxy phosphoryl anion ((CH3O)2PO(-)) was generated in the gas phase by ion-molecule reaction using phenyl nitrene anion radical (PhN(-)) to abstract a proton. Phenyl nitrene was generated by dissociative electron attachment with phenyl azide (PhN3) in a flowing afterglow apparatus. Using bracketing studies of ion-molecule reactions of (CH3O)2PO(-) with potential proton-donor molecules of known acidity, PA(CH3O)2PO(-)) was determined to be 358 + or - 2 kcal/mol and delta H sub f degree ((CH3O)2PO(-)) was calculated to be -207.3 + or - 2 kcal/mol. The electron affinity, EA((CH3O)2P(=O)), was also investigated using the bracketing technique and was found to be 2.2 + or - 0.1 eV. Reactions of (CH3O)2PO(-) with methyl halides indicates that the dimethoxy phosphoryl anion is an ambident species of low intrinsic nucleophilicity. (CH3O)2PO(-) reacts through electron transfer process with numerous halogenated alkanes. The dimethoxy phosphoryl anions has been found to form very stable hydrogen bonded complexes with various neutral organic and inorganic complexes. The reactions of the hydrogen bonded adduct of dimethyl phosphite and dimethoxy phosphoryl anion, (CH3O)2PO(-)/H(O=)P(OCH3)2, was also investigated with the same neutral substrates. Its reactions similar to those of the dimethoxy phosphoryl anion. Keywords: Reaction kinetics.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 13, 1986
- Accession Number
- ADA168816
Entities
People
- Krisma D. Dewitt