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Abstract Our efforts in the chemistry of gold complexes featuring ambiphilic phosphine‐carbenium L/Z‐type ligand have led us to consider the reduction of the carbenium moiety as a means to modulate the gold–carbenium interaction present in these complexes. Here, it was shown that the one‐electron reduction of [(o‐Ph2P(C6H4)Acr)AuCl]+(Acr=9‐N‐methylacridinium) produces a neutral stable radical, the structure of which showed a marked increase in the Au–Acr distance. Related structural changes were observed for the phosphine oxide analogue [(o‐Ph2P(O)(C6H4)Acr]+, the reduction of which interfered with the P=O→carbenium interaction. These structural effects, driven by a reduction‐induced change in the electronic and electrostatic characteristics of the compounds, showed that the charge and accepting properties of the carbenium unit can be modulated. These results highlight the redox‐noninnocence of carbenium Z‐type ligand, a feature that can be exploited to induce specific conformational changes.
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Metal→Carbon Dative Bonding
Abstract As part of our interest in unusual bonding situations, we are now targeting complexes featuring metal→carbon dative bonds. Here, we report on the formation of such linkages in a series of Group 10 complexes featuring a triarylphosphine ligand functionalized at the γ position by a carbenium ion. Through combined synthetic, spectroscopic, and computational studies, we show that the M→Ccarbeniuminteraction present in these complexes scales with the basicity of the donor, confirming its dative nature.
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- Award ID(s):
- 1856453
- PAR ID:
- 10371101
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 61
- Issue:
- 24
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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