A Heterobimetallic Journey from Ambiphilic Ti Phosphide to Nucleophilic Ti/Ir Phosphinidene
Abstract
Ambiphilic phosphides (PX2−) are a scarcely studied class of chemically non-innocent ligands in which the central phosphorus atom behaves both as a nucleophile and an electrophile. Here, we show that an ambiphilic Ti phosphide engages in successive rearrangements, yielding Ti/Ir and Ti/Rh heterobimetallic complexes with intriguing properties. For instance, complex 3Ir is a highly active hydrosilylation catalyst for carbonyl compounds with Turnover Numbers (TONs) of up to 47 500. Trimetallic Au/Ti/Ir and Fe/Ti/Ir complexes 4 and 5 were also synthesized. In addition, we report complex 7, the first structurally characterized example of a Group 4/Group 9 bridging phosphinidene, which is also highly pyramidalized and nucleophilic. The bonding situation in these complexes was studied using intrinsic bonding orbitals (IBOs) and the Quantum Theory of Atoms In Molecules (QTAIM) analysis. The correlation between the delocalization index (DI) and the penetration index (p) defines an ionicity parameter (ι) and a bonding threshold (BT), such that p = ι·DI + BT. Two atoms with p < 90% should be considered non-bonded. Within this conceptual framework, the interactions studied in this paper (Ti–Ir, Ti–Rh, Ti–P and Ir–P) correspond to more or less ionic flavors of dative bonds.
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BibTeX
@article{moerman2026heterobimetallic,
title = {{A Heterobimetallic Journey from Ambiphilic Ti Phosphide to Nucleophilic Ti/Ir Phosphinidene}},
author = {Alex Moerman and Adrien T. Normand and Hélène Cattey and Maxime Sauvageot and Viktoria P Bothe and Mehmet Jahja and Anna Krystianiak and E. Daiann Sosa Carrizo and Paul Fleurat-Lessard and Pierre Le Gendre},
journal = {Chemical Science},
year = {2026},
month = sep,
doi = {10.1039/d6sc04689d},
url = {https://hal.science/hal-05786613v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - A Heterobimetallic Journey from Ambiphilic Ti Phosphide to Nucleophilic Ti/Ir Phosphinidene
AU - Alex Moerman
AU - Adrien T. Normand
AU - Hélène Cattey
AU - Maxime Sauvageot
AU - Viktoria P Bothe
AU - Mehmet Jahja
AU - Anna Krystianiak
AU - E. Daiann Sosa Carrizo
AU - Paul Fleurat-Lessard
AU - Pierre Le Gendre
PY - 2026
DA - 2026/09/29
JO - Chemical Science
DO - 10.1039/d6sc04689d
UR - https://hal.science/hal-05786613v1
AB - Ambiphilic phosphides (PX2−) are a scarcely studied class of chemically non-innocent ligands in which the central phosphorus atom behaves both as a nucleophile and an electrophile. Here, we show that an ambiphilic Ti phosphide engages in successive rearrangements, yielding Ti/Ir and Ti/Rh heterobimetallic complexes with intriguing properties. For instance, complex 3Ir is a highly active hydrosilylation catalyst for carbonyl compounds with Turnover Numbers (TONs) of up to 47 500. Trimetallic Au/Ti/Ir and Fe/Ti/Ir complexes 4 and 5 were also synthesized. In addition, we report complex 7, the first structurally characterized example of a Group 4/Group 9 bridging phosphinidene, which is also highly pyramidalized and nucleophilic. The bonding situation in these complexes was studied using intrinsic bonding orbitals (IBOs) and the Quantum Theory of Atoms In Molecules (QTAIM) analysis. The correlation between the delocalization index (DI) and the penetration index (p) defines an ionicity parameter (ι) and a bonding threshold (BT), such that p = ι·DI + BT. Two atoms with p < 90% should be considered non-bonded. Within this conceptual framework, the interactions studied in this paper (Ti–Ir, Ti–Rh, Ti–P and Ir–P) correspond to more or less ionic flavors of dative bonds.
SN - 2041-6520
SN - 2041-6539
ER -