Gas electron diffraction then and now: from trisilyl phosphine to iso-propyl(tert-butyl)(trichlorosilyl)phosphine. Issue 46 (21st October 2021)

• Record Type: Journal Article
• Authors: Wagner, Isabella; Rankin, David W. H.; Masters, Sarah L.
• Is Part Of: Dalton transactions. Volume 50:Issue 46(2021)
• Page Start: 17000
• Page End: 17007
• Publication Date: 2021-10-21
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt02888j
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : GED has evolved hugely in the 50 years of Dalton Transactions. Combining experimental and theoretical data now allows complicated structures free from intermolecular interactions like iso-propyl( tert -butyl)(trichlorosilyl)phosphine to be revealed. Abstract : The gas-phase molecular structure of iso-propyl( tert -butyl)(trichlorosilyl)phosphine has been determined using a combination of gas electron diffraction and computational methods. The structure presents a conformational challenge that required use of the SARACEN method to combine theoretical observations into the least-squares refinement process, a great advance on the techniques used to solve the structure of the parent trisilyl phosphine. Five conformers were found on the potential-energy surface for iso-propyl( tert -butyl)(trichlorosilyl)phosphine using the UCONGA program, and following a series of individual structure refinements a combined model with the two most abundant confirmers was evaluated. Key structural parameters ( r a ) include r P–Si [225.5(6) pm], r Si–Clmean [204.0(1) pm] and r P–Cmean [204.0(1) pm], ∠P–C–H 101.5(5)°, ∠C–C–C (iPr) 110.5(5)°, ∠C–C–C ( t Bu) 109.2(5)° and ∠C–P–C 105.4(5)°.