Martin’s spirophosphorane: a platform for the design of [OPO] pincer ligands and their group 4 complexes
Martin’s well-known spirophosphorane (1) has been transformed into a series of [OPO] pincer-type ligand motifs via three distinct pathways. In the first pathway, upon deprotonation of 1, treatment with suitably chosen lithium alkyl, aryl, or amido reagents induced a double ring expansion, affording...
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| Main Authors: | , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2026
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| In: |
Inorganic chemistry
Year: 2026, Volume: 65, Issue: 1, Pages: 736-746 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.5c05056 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1021/acs.inorgchem.5c05056 Verlag, kostenfrei, Volltext: https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c05056 
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| Author Notes: | Jean-Marc Mörsdorf, Lukas Eberle, Benjamin Rudin, Sebastian Senn, Lutz H. Gade, and Joachim Ballmann |
| Summary: | Martin’s well-known spirophosphorane (1) has been transformed into a series of [OPO] pincer-type ligand motifs via three distinct pathways. In the first pathway, upon deprotonation of 1, treatment with suitably chosen lithium alkyl, aryl, or amido reagents induced a double ring expansion, affording an open-chain λ3-phosphane. The second pathway proceeded through reductive cleavage of the bicyclic scaffold, yielding a dimeric, formally trianionic [OPO] framework that, upon controlled monoprotonation, furnished a dianionic [OPO] dilithium salt incorporating a P−H unit. Complexation of this ligand via salt metathesis with Ti(NMe2)2Cl2 induced one dimethylamino substituent at the titanium center to act as an intramolecular Brønsted base, effecting deprotonation of the P−H group and thereby generating a titanium complex featuring a formally trianionic [OPO] pincer ligand. The third pathway demonstrated that spirophosphorane 1 could act directly as a ligand precursor. Reaction with homoleptic group 4 alkyl or amido complexes triggered−upon deprotonation−an intramolecular migration of an alkyl or amido moiety to the phosphorus, initiating a double ring expansion and giving the corresponding [OPO]-coordinated complexes. The mechanistic details of these transformations were elucidated by DFT analysis for the reaction of ZrBn4 with 1. |
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| Item Description: | Online veröffentlicht: December 23, 2025 Gesehen am 20.04.2026 |
| Physical Description: | Online Resource |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.5c05056 |