4 years ago

Structural Variability of R2C Adducts of 3a,6a-Diaza-1,4-diphosphapentalene: Tuning the NP Bonding

Structural Variability of R2C Adducts of 3a,6a-Diaza-1,4-diphosphapentalene: Tuning the NP Bonding
Evgenii V. Baranov, Alla V. Arapova, Vadim E. Galperin, Yulia S. Panova, Gleb A. Abakumov, Georgy K. Fukin, Alexander N. Kornev
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).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/zaac.201700223

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