Isolation of a phosphinidene sulfide and selenide †

Journal article

We describe the synthesis of an isolable phosphinidene sulfide and phosphinidene selenide (BnArNP 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 Ch; Ch = S, Se) by reaction of a sterically protected phosphinidene oxide (BnArNPO) with Lawesson's or Woollins' reagents, respectively. These compounds reveal short PE bonds consistent with a high degree of pπ–pπ double bond character. The pendant amido group on the phosphorus atom plays an important role in their stabilization through nitrogen lone pair donation into the P–Ch π* orbital, and evidence for isomerism about the N–P bond was observed for both species. Dimeric intermediates featuring mixed phosphorus(iii)/phosphorus(v) centers could be isolated and structurally authenticated during the course of these studies providing some insight into the mechanism of formation of the titular compounds.

Authors: Hu, C; Pink, M; Goicoechea, JM

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Royal Society of Chemistry
• Journal: Chemical Science
• Publication date: 2025-07-10
• Acceptance date: 2025-07-09
• DOI: 10.1039/d5sc04352b
• EISSN: 2041-6539
• ISSN: 2041-6520
• Language: English