NHC‐Copper(I)‐Mediated Functionalization of White Phosphorus
- 1Institute of Inorganic Chemistry University of Regensburg Regensburg Germany
Abstract
We report a method for converting white phosphorus (P4) directly into tetra‐ and pentaphosphanes using N‐heterocyclic carbene (NHC) copper(I) complexes. The insertion of P4 into the metal‐element bonds of the NHC complexes (6Dipp)Cu(Nu) [Nu = OtBu and N(iPr)2] affords [(6Dipp)Cu(κ 2‐P4OtBu)] (1) and [(6Dipp)Cu{κ 2‐P4N(iPr)2}] (3), which exhibit rotation of the [P4Nu]− ligand around the copper center in solution. This fluxional process is suppressed at low temperature, as shown by variable‐temperature 31P{1H} NMR spectroscopy. Treatment of 1 with W(CO)5(thf) resulted in the formation of the bimetallic complex [(6Dipp)Cu(μ,κ 2:κ 1‐P4OtBu){W(CO)5}] (2) which does not show fluxional behavior. Reactions of 1 and 3 with p‐block element halides release metal‐free asymmetrically substituted bicyclo[1.1.0]tetraphosphabutane ‘butterfly’ compounds. The polyphosphanes P4(PMes2)(OtBu) (4a), P4[P{N(iPr)2}2](OtBu) (4b), P4[P{N(iPr)2}2]{N(iPr)2} (4c), and P4(BPh2){N(iPr)2} (5) were isolated as stable compounds. Treatment of 4c with the NHC IMes induces further phosphorus–phosphorus bond cleavage and rearrangement to give NHC‐phosphinidene adduct [cyclo‐P3{N(iPr)2}(P{N(iPr)2}2)(P═IMes)] (6). Compound 4c also reacts with W(CO)5(thf) and CuBr·SMe2 to give coordination complexes [W(CO)5{κ 1‐P4(P{N(iPr)2}2)(N{iPr}2)}] (7) and [Cu(Br){κ 2‐P4(P{N(iPr)2}2)(N{iPr}2)}] (8), respectively, demonstrating the ability of 4c to serve as a mono‐ and bidentate ligand for transition metals. All compounds were characterized crystallographically and spectroscopically.
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BibTeX
@article{downie2026nhccopperimediated,
title = {{NHC‐Copper(I)‐Mediated Functionalization of White Phosphorus}},
author = {Thomas M. Horsley Downie and Sophia A. Vogler and Gábor Balázs and Francesco Cirigliano and Robert Wolf},
journal = {Angewandte Chemie (International Ed. in English)},
year = {2026},
month = sep,
doi = {10.1002/anie.8252739},
url = {https://doi.org/10.1002/anie.8252739},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - NHC‐Copper(I)‐Mediated Functionalization of White Phosphorus
AU - Thomas M. Horsley Downie
AU - Sophia A. Vogler
AU - Gábor Balázs
AU - Francesco Cirigliano
AU - Robert Wolf
PY - 2026
DA - 2026/09/18
JO - Angewandte Chemie (International Ed. in English)
DO - 10.1002/anie.8252739
UR - https://doi.org/10.1002/anie.8252739
AB - We report a method for converting white phosphorus (P4) directly into tetra‐ and pentaphosphanes using N‐heterocyclic carbene (NHC) copper(I) complexes. The insertion of P4 into the metal‐element bonds of the NHC complexes (6Dipp)Cu(Nu) [Nu = OtBu and N(iPr)2] affords [(6Dipp)Cu(κ 2‐P4OtBu)] (1) and [(6Dipp)Cu{κ 2‐P4N(iPr)2}] (3), which exhibit rotation of the [P4Nu]− ligand around the copper center in solution. This fluxional process is suppressed at low temperature, as shown by variable‐temperature 31P{1H} NMR spectroscopy. Treatment of 1 with W(CO)5(thf) resulted in the formation of the bimetallic complex [(6Dipp)Cu(μ,κ 2:κ 1‐P4OtBu){W(CO)5}] (2) which does not show fluxional behavior. Reactions of 1 and 3 with p‐block element halides release metal‐free asymmetrically substituted bicyclo[1.1.0]tetraphosphabutane ‘butterfly’ compounds. The polyphosphanes P4(PMes2)(OtBu) (4a), P4[P{N(iPr)2}2](OtBu) (4b), P4[P{N(iPr)2}2]{N(iPr)2} (4c), and P4(BPh2){N(iPr)2} (5) were isolated as stable compounds. Treatment of 4c with the NHC IMes induces further phosphorus–phosphorus bond cleavage and rearrangement to give NHC‐phosphinidene adduct [cyclo‐P3{N(iPr)2}(P{N(iPr)2}2)(P═IMes)] (6). Compound 4c also reacts with W(CO)5(thf) and CuBr·SMe2 to give coordination complexes [W(CO)5{κ 1‐P4(P{N(iPr)2}2)(N{iPr}2)}] (7) and [Cu(Br){κ 2‐P4(P{N(iPr)2}2)(N{iPr}2)}] (8), respectively, demonstrating the ability of 4c to serve as a mono‐ and bidentate ligand for transition metals. All compounds were characterized crystallographically and spectroscopically.
SN - 1433-7851
SN - 1521-3773
ER -