Reactivity of a phosphaalumene towards heteroallenes
- 1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
- 2Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
- 3Leibniz Institute for Catalysis e.V. (LIKAT) A.-Einstein-Str. 29a 18059 Rostock Germany
Abstract
Exposure of DipTerPAlCp* (1) to CO2 at ambient temperature results in the formation of DipTerPCO (2) along with the formation of (Cp*AlO)x. Isolating 2 in crystalline form is challenging, often resulting in mixtures with its dimer (DipTerPCO)2 (2dim), which was crystallographically characterized. A [2 + 2] cyclization product of 1 and 2 was crystallographically identified as the cyclic diphosphaurea derivative [(DipTerP)2(µ-AlCp*)(µ-CO)] (3), which shows a planar P2AlC ring. 2 also reacts with an NHC-stabilized boraketene via CO-elimination, giving the oxaborirane 4, featuring a planar BOCP unit with a localized P
Created by potrace 1.16, written by Peter Selinger 2001-2019
C double bond. Additionally, the reactivity of 1 towards diisopropylcarbodiimide (DIC) was explored. Treatment of 1 with DIC resulted in the formation of DipTerP[C(NiPr)2]Al[C(NiPr)2]Cp* (5), featuring a PCNAl four-membered ring with an additional Cp*-substituted amidinate ligand on the Al atom. This amidinate substituent results from insertion of a second DIC molecule into the Al–Cp* bond. Heating a solution of 5 results in a thermodynamically driven rearrangement to aluminium phosphaguanidinate complex 6 with a PC double bond. Compound 6 is best classified as an phosphaguanidinate or as an inversely polarized phosphaalkene, which is supported by NMR data and DFT calculations. Upon hydrolysis 5 and 6 decompose cleanly to give phosphaguanidine DipTerP(H)C(NHiPr)NiPr (7) with the concomitant formation of a trimeric aluminoxan. This study demonstrates the potential of phosphaalumene 1 as a synthon for aryl phosphaketenes, which themselves enable the synthesis of novel heterocyclic structures. Moreover, the reactivity towards DIC differs considerably from that of related phosphagallenes, enabled by the lability of the Al–Cp* bond.
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BibTeX
@article{wellnitz2026reactivity,
title = {{Reactivity of a phosphaalumene towards heteroallenes}},
author = {Tim Wellnitz and Jakob Boardman and Paul Fritsche and Yannick Konrad and Diana Bröllos and Samuel Nees and Holger Braunschweig and Christian Hering-Junghans},
journal = {Chemical Science},
year = {2026},
month = aug,
doi = {10.1039/d6sc04181g},
url = {https://doi.org/10.1039/d6sc04181g},
note = {CC BY 3.0},
}
RIS
TY - JOUR
TI - Reactivity of a phosphaalumene towards heteroallenes
AU - Tim Wellnitz
AU - Jakob Boardman
AU - Paul Fritsche
AU - Yannick Konrad
AU - Diana Bröllos
AU - Samuel Nees
AU - Holger Braunschweig
AU - Christian Hering-Junghans
PY - 2026
DA - 2026/08/31
JO - Chemical Science
DO - 10.1039/d6sc04181g
UR - https://doi.org/10.1039/d6sc04181g
AB - Exposure of DipTerPAlCp* (1) to CO2 at ambient temperature results in the formation of DipTerPCO (2) along with the formation of (Cp*AlO)x. Isolating 2 in crystalline form is challenging, often resulting in mixtures with its dimer (DipTerPCO)2 (2dim), which was crystallographically characterized. A [2 + 2] cyclization product of 1 and 2 was crystallographically identified as the cyclic diphosphaurea derivative [(DipTerP)2(µ-AlCp*)(µ-CO)] (3), which shows a planar P2AlC ring. 2 also reacts with an NHC-stabilized boraketene via CO-elimination, giving the oxaborirane 4, featuring a planar BOCP unit with a localized P Created by potrace 1.16, written by Peter Selinger 2001-2019 C double bond. Additionally, the reactivity of 1 towards diisopropylcarbodiimide (DIC) was explored. Treatment of 1 with DIC resulted in the formation of DipTerP[C(NiPr)2]Al[C(NiPr)2]Cp* (5), featuring a PCNAl four-membered ring with an additional Cp*-substituted amidinate ligand on the Al atom. This amidinate substituent results from insertion of a second DIC molecule into the Al–Cp* bond. Heating a solution of 5 results in a thermodynamically driven rearrangement to aluminium phosphaguanidinate complex 6 with a PC double bond. Compound 6 is best classified as an phosphaguanidinate or as an inversely polarized phosphaalkene, which is supported by NMR data and DFT calculations. Upon hydrolysis 5 and 6 decompose cleanly to give phosphaguanidine DipTerP(H)C(NHiPr)NiPr (7) with the concomitant formation of a trimeric aluminoxan. This study demonstrates the potential of phosphaalumene 1 as a synthon for aryl phosphaketenes, which themselves enable the synthesis of novel heterocyclic structures. Moreover, the reactivity towards DIC differs considerably from that of related phosphagallenes, enabled by the lability of the Al–Cp* bond.
SN - 2041-6520
SN - 2041-6539
ER -