Catalytic hydrophosphination of alkynes using structurally diverse sodium diphenylphosphide donor complexes

Tools

Whitelaw, Michael T. and Banerjee, Sumanta and Kennedy, Alan R. and van Teijlingen, Alexander and Tuttle, Tell and Mulvey, Robert E. (2022) Catalytic hydrophosphination of alkynes using structurally diverse sodium diphenylphosphide donor complexes. Cell Reports Physical Science, 3 (7). 100942. ISSN 2666-3864 (https://doi.org/10.1016/j.xcrp.2022.100942)

[thumbnail of Whitelaw-etal-CRPS-2022-Catalytic-hydrophosphination-of-alkynes]
Preview
 Text. Filename: Whitelaw_etal_CRPS_2022_Catalytic_hydrophosphination_of_alkynes.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (6MB)| Preview

Abstract

Currently, there is a drive to develop the organoelement chemistry of sodium, the most abundant alkali metal on earth, as an alternative to that of rarer lithium, with the prime focus on sustainability. Organolithium compounds have been essential to the success of synthetic chemistry for more than a century, although their implementation has been essentially confined to stoichiometric synthesis. Here, we report on synthetic, structural, catalytic, mechanistic, and theoretical studies of a series of sodium diphenylphosphides, having unique structures defined by the Lewis base donor D solvating the Lewis acidic sodium cation. These donor complexes are explored as hydrophosphination catalysts on reacting Ph 2P–H with a range of alkynes and prove to be generally effective under ambient conditions, especially when n = 1 in [{Ph 2PNa(D) x} n]. Density functional theory (DFT) studies have shed light on the possible mechanisms of these catalytic cycles and how they relate to the E, Z, or α isomer formed.

ORCID iDs

Whitelaw, Michael T., Banerjee, Sumanta, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, van Teijlingen, Alexander ORCID logoORCID: https://orcid.org/0000-0002-3739-8943, Tuttle, Tell and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:80935
    Dates:
    Date
    Event
    20 July 2022
    Published
    21 June 2022
    Published Online
    26 May 2022
    Accepted
    Notes:'Standard' and 'Extended' versions of this research article are available.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:31 May 2022 14:07
    Last modified:16 Dec 2024 02:33
    URI:https://strathprints.strath.ac.uk/id/eprint/80935
CORE (COnnecting REpositories)