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- Title
Reaction of bis(dialkylphosphino)amines R<sub>2</sub>PNHPR<sub>2</sub> (R = i-Pr, t-Bu, Ph) with halogens X<sub>2</sub> (X = Cl, Br, I): different solvents – different stories.
- Authors
Riley, Robert D.; Robertson, Katherine N.; Clyburne, Jason A.C.
- Abstract
The bis(dialkylphosphino)amines R2PNHPR2 react with elemental halogens X2 in dichloromethane to produce cationic products of the general form [(R)2P(X)-N-(R)2P(X)]+ (R = i-Pr, Ph, and t-Bu; X = Cl, Br, and I). All of the nine possible products have been isolated and characterized using X-ray diffraction. The dichloro compounds crystallize as [HCl2]− salts, while the dibromo and diiodo products have been isolated as trihalides, [X3]−. A number of these compounds have been shown to react further with methanol to produce salts containing [(R)2P(OCH3)N(R)2P(OCH3)]+ cations, some of which have also been characterized using X-ray crystallography. The conversion of [(Ph)2P(I)-N-(Ph)2P(I)][I3] to [(Ph)2P(OCH3)-N-(Ph)2P(OCH3)][I3] was monitored using 31P NMR spectroscopy that revealed a stepwise reaction of the former compound with methanol. The results are discussed within the context of coupled reactions; this is then used to rationalize a mechanism for the formation of a rare catenated bismuth compound we reported previously. We suggest that the formation of the weak Bi–Bi bonds is offset by a coupled or a connected reaction mechanism, involving an irreversible reaction forming strong P–OR bonds in another of the isolated products.
- Subjects
HALOGENS; AMINES; X-ray crystallography; NUCLEAR magnetic resonance spectroscopy; BISMUTH compounds; DICHLOROMETHANE; BISMUTH
- Publication
Canadian Journal of Chemistry, 2022, Vol 100, Issue 10, p737
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/cjc-2022-0095