Reactivity of Sodium Pentaphospholide Na[cyclo-P5 ] towards C≡E (E=C, N, P) Triple Bonds

Andrey Petrov; Lawrence Conrad; Nathan T Coles; Manuela Weber; Dirk Andrae; Almaz Zagidullin; Vasili Miluykov; Christian Müller

doi:10.1002/chem.202203056

Reactivity of Sodium Pentaphospholide Na[cyclo-P₅ ] towards C≡E (E=C, N, P) Triple Bonds

Chemistry. 2022 Dec 1;28(67):e202203056. doi: 10.1002/chem.202203056. Epub 2022 Nov 15.

Authors

Andrey Petrov¹, Lawrence Conrad², Nathan T Coles^{1

3}, Manuela Weber¹, Dirk Andrae², Almaz Zagidullin⁴, Vasili Miluykov⁴, Christian Müller¹

Affiliations

¹ Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
² Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195, Berlin, Germany.
³ School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
⁴ Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, Kazan, Russia.

Abstract

A diglyme solution of Na[cyclo-P₅ ] (1) reacts with alkynes and isolobal nitriles and phosphaalkynes to afford the otherwise elusive (aza)phospholide anions 2 a-c, 4 a,b, and 6. The reaction of Na[cyclo-P₅ ] with alkynes and nitriles was studied by means of DFT methods, which suggested a concerted mechanism for the formation of 2 a and 4 b. The anions 2 a-c, 4 a,b, and 6 coordinate in an η⁵ -fashion towards Fe^II to give the sandwich (aza)phosphametallocenes 3 a-c, 5 a,b and 7 in moderate to good yields. The new compounds were characterized by means of multinuclear NMR spectroscopy, single-crystal X-ray diffraction and cyclic voltammetry.

Keywords: DFT calculations; X-ray diffraction; cyclic voltammetry; heteroferrocenes; phosphorus heterocycles.