Chemical properties of 3a,6a-diaza-1,4-diphosphapentalene. Addition of polyhalohydrocarbons
- Authors: Kornev A.N.1, Galperin V.E.1, Sushev V.V.1, Panova Y.S.1, Fukin G.K.1, Cherkasov A.V.1, Abakumov G.A.1
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Affiliations:
- G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
- Issue: Vol 65, No 11 (2016)
- Pages: 2658-2667
- Section: Full Articles
- URL: https://journals.rcsi.science/1066-5285/article/view/239325
- DOI: https://doi.org/10.1007/s11172-016-1632-4
- ID: 239325
Cite item
Abstract
3a,6a-Diaza-1,4-diphosphapentalene (DDP, 1), in contrast to common azaphospholes, readily reacts with polyhalohydrocarbons with the formation of 1,1- or 1,4-addition products at the phosphorus atoms. Dibromomethane gives the substitution product of two bromine atoms [CH2(DDP)2]Br2 (2) and diphosphine (DDP-DDP)Br2 (3) containing a bridging bromine atom. In the course of the reaction of DDP with CF2Br2, two products of sequential substitution of the bromine atoms were isolated, which are 1,4-Br2(DDP) (6) and [CF2(DDP)2]Br2 (7). Tris(pentafluorophenyl)phosphine reacts with DDP at the C—F bond with the formation of 1,1-addition product 8. Compounds 2, 3, 7, and 8 contain hypervalent (tervalent 4-coordinated) phosphorus atoms. X-ray diffraction data indicate that the mutual arrangement of the DDP fragments in compounds 2, 3, and 7 is determined by the non-covalent interaction of one of the bromine atoms simultaneously with two phosphorus atoms of different DDP fragments in such a way that the lines of the N—P bonds converge at this bromine atom.
About the authors
A. N. Kornev
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Author for correspondence.
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137
V. E. Galperin
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137
V. V. Sushev
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137
Yu. S. Panova
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137
G. K. Fukin
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137
A. V. Cherkasov
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137
G. A. Abakumov
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
Email: akornev@iomc.ras.ru
Russian Federation, 49 ul. Tropinina, Nizhny Novgorod, 603137