Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Metal complexes of a structurally embellished phosphinane ligand: an assessment of stereoelectronic effects

Edwards, Peter G. ORCID:, Kariuki, Benson ORCID:, Limon, Matthieu Deniel, Ooi, Liling, Platts, James Alexis ORCID: and Newman, Paul David ORCID: 2011. Metal complexes of a structurally embellished phosphinane ligand: an assessment of stereoelectronic effects. European Journal of Inorganic Chemistry 2011 (8) , pp. 1230-1239. 10.1002/ejic.201001170

Full text not available from this repository.


The stereoelectronic features of the pentacyclic phosphane (1S,4R,4aS,5aR,6R,9S,9aS,10aR)-4,6,11,11,12,12-hexamethyl-10-phenyldodecahydro-1,4:6,9-dimethanophenoxaphosphinine (phenop) have been explored through a range of empirical methods including single-crystal X-ray structure determinations of the sulfide derivative phenopS (1), the selenide phenopSe (2), [Fe(CO)4(κ1-phenop)] (3), [W(CO)5(κ1-phenop)] (4) and trans-[Rh(κ1-phenop)(CO)Cl] (5). Cone angles derived from the structural data range from 164–203° with the smaller values being observed for the compounds possessing a phenyl group that is orthogonal to the P–Z bond and the larger values for the compounds expressing a parallel phenyl ring orientation. The cone angle data suggest a moderately bulky phosphane comparable, in steric terms, to PCy3. This is further borne out on inspection of the M–P bond lengths which tend towards the longer end of the known scale. Some flexibility is observed in the central ring which approximates to a boat conformation at one extreme and an envelope at the other depending on the nature of the P-substituent. The electronic properties of κ1-phenop have been assessed using a combination of infrared and NMR spectroscopy. The absolute value of the one-bond coupling constants 1JP-Se and 1JP-Rh are very close to those reported for PPh3, suggesting a close analogy between κ1-phenop and the well known triphenylphosphane. In addition, relevant υ(CO) stretches in the IR spectra of the metal carbonyl complexes also closely mimic those for the analogous complexes containing PPh3. These conclusions are supported by molecular electrostatic potential calculations at the DFT level which place phenop close to PPh3 in terms of lone pair availability

Item Type: Article
Date Type: Publication
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: P ligands ; Phosphinane ligand ; Phosphorus heterocycles ; Carbonyl li­gands
Publisher: Wiley-Blackwell
ISSN: 1434-1948
Last Modified: 02 Dec 2022 12:10

Citation Data

Cited 3 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item