In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2003, No. 2 ( 2003-01), p. 249-254
Abstract:
The reaction of NapP 2 S 4 ( 1 ; Nap = naphthalene‐1,8‐diyl) with chlorine gas gave [Nap(PCl 2 )(PCl 4 )] ( 2 ), displaying a rare σ 4 P‐σ 6 P bonding interaction. An X‐ray structure analysis confirmed the PCl 5 ‐like, P−P bond containing phosphonium‐phosphoride structure of 2 in the crystal, which was also found in solution at low temperature. At ambient and higher temperatures, dynamic behaviour on the NMR time‐scale was observed, which was assigned to interchange of the ionic phosphonium‐phosphoride form 2 and the molecular bis(phosphorane) Nap(PCl 3 ) 2 form 3 , rather than to the ionic phosphonium salt‐phosphorane form [Nap(PCl 3 )(PCl 2 )][Cl] 4 . Electronic structure calculations were performed at the B3LYP/6−31G(d,p) level of theory on structures 2 and 3 ; structure 3 was located as a local minimum on the potential energy surface, 15 kcal·mol −1 higher in energy than structure 2 . The crystal structure and calculated P−P distances are 2.34 and 2.31 Å for 2 and 3 , respectively. An activation energy of 19.7 kcal·mol −1 was found for the transition state structure by coordinate driving calculations; the line‐shape analysis of variable temperature 31 P{ 1 H} NMR spectra gave an activation energy of 14.4 kcal·mol −1 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2003:2
DOI:
10.1002/ejic.200390033
Language:
English
Publisher:
Wiley
Publication Date:
2003
detail.hit.zdb_id:
1475009-0
Permalink