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1,1‐ and 1,4‐Addition Reactions with 3a,6a‐Diaza‐1,4‐diphosphapentalene Containing Two‐Coordinate and Formally Divalent Phosphorus
Author(s) -
Kornev Alexander N.,
Galperin Vadim E.,
Sushev Vyacheslav V.,
Zolotareva Natalia V.,
Baranov Evgenii V.,
Fukin Georgy K.,
Abakumov Gleb A.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600348
Subject(s) - chemistry , hypervalent molecule , phosphorus , divalent , substrate (aquarium) , chloride , inorganic chemistry , salt (chemistry) , ion , covalent bond , medicinal chemistry , organic chemistry , reagent , oceanography , geology
3a,6a‐Diaza‐1,4‐diphosphapentalene (DDP) reacts with halocarbons to give addition products to one or both phosphorus atoms depending on the substrate. Chlorotriphenylmethane affords a 1,4‐addition product, which slowly decomposes in solution to form the Ph 3 C radical and the chloro‐DDP coupling product with a P–P bond. Benzyl chloride is added to one phosphorus atom to form hypervalent (trivalent, four‐coordinate) phosphorus with a N ··· P distance (nonvalent interaction) of 2.191(2) Å. A workup of the latter with GeCl 2 results in a complex salt containing the GeCl 3 – anion and cation with covalent N–P bonding.