Structural Variability of R2C Adducts of 3a,6a‐Diaza‐1,4‐diphosphapentalene: Tuning the N→P Bonding

3a,6a‐Diaza‐1,4‐diphosphapentalene (DDP) reacts with hexachlorocyclopentadiene to form a stable adduct (ClC)4C=DDP (4). The phosphorus atom involved into coordination has a pyramidal arrangement but retains partial double bonding with carbon [1.752(3) Å]. At the same time, the P–N bond remains coval...

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Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) 2017-10, Vol.643 (19), p.1208-1214
Main Authors: Kornev, Alexander N., Galperin, Vadim E., Panova, Yulia S., Arapova, Alla V., Baranov, Evgenii V., Fukin, Georgy K., Abakumov, Gleb A.
Format: Article
Language:English
Subjects:
Addition reaction
Adducts
Azaphospholes
Bonding
Electronegativity
Hypervalent phosphorus
Malononitrile
Phosphorus ylides
X‐ray diffraction
Zwitterions
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Summary:3a,6a‐Diaza‐1,4‐diphosphapentalene (DDP) reacts with hexachlorocyclopentadiene to form a stable adduct (ClC)4C=DDP (4). The phosphorus atom involved into coordination has a pyramidal arrangement but retains partial double bonding with carbon [1.752(3) Å]. At the same time, the P–N bond remains covalent [1.824(3) Å]. The adduct 4 is better described as a zwitterionic compound with strongly delocalized positive and negative charges. A similar zwitterionic adduct DDP=C(CN)2 was prepared by the reactions of dichloro‐DDP (7) with malononitrile in the presence of Et3N. DFT calculations showed that related structures are formed in the case of the substituents (ClC)4C=, (HC)4C=, (NC)2C=, and (MeCO)2C=, possessing electron‐delocalizing properties. Compounds with other R2C groups (R = Ph, Me, C6F5, Cl), possessing electronegative properties as well, but insufficient e‐delocalization, demonstrate the noncovalent P–N bonding and a little shorter R2C–P bond lengths (ca. 1.70 Å).
ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.201700223