Isolation of arylhalodiphosphenes: periodic trends in R–P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 P–X bonding (X = Cl, Br, I)

Wenger, JS; Gaschik, N; Rowe, WJ; Crumpton, AE; van IJzendoorn, B; Mehta, M

Journal article

Isolation of arylhalodiphosphenes: periodic trends in R–P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 P–X bonding (X = Cl, Br, I)

Abstract:: For over a century, aryldiazonium halides have served as widely used building blocks within synthetic chemistry. They are vital intermediates in converting simple anilines to high-value products, including those needed to prepare pharmaceuticals, dyes, and functional materials. Despite the prevalence of these nitrogen-based organic salts in laboratories, structurally related phosphorus-based salts remain scarce. Herein, we report the isolation and structural characterization of a monomeric arylchlorodiphosphene, (MsFluInd*)PPCl·(Et2O)2 (where MsFluInd* is a sterically demanding hydrindacene substituent), for the first time. The structure and reactivity of (MsFluInd*)PPCl were explored to compare the novel arylhalodiphosphene with compositionally related aryldiazonium chlorides, [RNN][Cl], and chloroiminophosphanes, RNPCl. The P–P bond of (MsFluInd*)PPCl was cleaved via protonolysis to afford the parent phosphine, (MsFluInd*)PH2. Halogen-exchange reactions between (MsFluInd*)PPCl and TMSX (TMS = trimethylsilyl, X = Br, I) afforded the related monomeric arylhalodiphosphenes, (MsFluInd*)PPX (X = Br, I). Finally, the coordination complex, [(MsFluInd*)PPCl·Ag][CF3SO3], was isolated by treatment of (MsFluInd*)PPCl with AgCF3SO3. Periodic trends in the structure and bonding of (MsFluInd*)PPX (X = Cl, Br, I) were investigated with spectroscopic, crystallographic, and computational methods. These studies confirm that the {PPX} moeity consists of a formal P–P double bond, and polar covalent P–X (X = Cl, Br, I) single bonds. (MsFluInd*)PPX (X = Cl, Br, I) represent the first fully characterized, crystalline arylhalodiphosphenes and serve to advance the state of low-coordinate phosphorus chemistry.

Publication status:: Published

Peer review status:: Peer reviewed

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APA Style

Wenger, J. S., Gaschik, N., Rowe, W. J., Crumpton, A. E., van IJzendoorn, B., & Mehta, M. (2026). Isolation of arylhalodiphosphenes: periodic trends in R–P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 P–X bonding (X = Cl, Br, I). Chemical Science.

MLA Style

Wenger, JS, et al. “Isolation of Arylhalodiphosphenes: Periodic Trends in R–P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 P–X Bonding (X = Cl, Br, I).” Chemical Science, 2026.

Chicago Style

Wenger, JS, N Gaschik, WJ Rowe, AE Crumpton, B van IJzendoorn, and M Mehta. 2026. “Isolation of Arylhalodiphosphenes: Periodic Trends in R–P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 P–X Bonding (X = Cl, Br, I).” Chemical Science.
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