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Abstract Reaction of (P)AuOTf [P=P(t‐Bu)2o‐biphenyl] with indenyl‐ or 3‐methylindenyl lithium led to isolation of gold η1‐indenyl complexes (P)Au(η1‐inden‐1‐yl) (1 a) and (P)Au(η1‐3‐methylinden‐1‐yl) (1 b), respectively, in >65 % yield. Whereas complex1 bis static, complex1 aundergoes facile, degenerate 1,3‐migration of gold about the indenyl ligand (ΔG≠153K=9.1±1.1 kcal/mol). Treatment of complexes1 aand1 bwith (P)AuNTf2led to formation of the corresponding cationic bis(gold) indenyl complexestrans‐[(P)Au]2(η1,η1‐inden‐1,3‐yl) (2 a) andtrans‐[(P)Au]2(η1,η2‐3‐methylinden‐1‐yl) (2 b), respectively, which were characterized spectroscopically and modeled computationally. Despite the absence of aurophilic stabilization in complexes2 aand2 b, the binding affinity of mono(gold) complex1 atoward exogenous (P)Au+exceed that of free indene by ~350‐fold and similarly the binding affinity of1 btoward exogenous (P)Au+exceed that of 3‐methylindene by ~50‐fold. The energy barrier for protodeauration of bis(gold) indenyl complex2 awith HOAc was ≥8 kcal/mol higher than for protodeauration of mono(gold) complex1 a.
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This content will become publicly available on January 15, 2027
Reactivity of gold and copper acetylide with a secondary borane
Bis(1-methyl-ortho-carboranyl)borane reacts with PPh3Au acetylide to give an η2-1-borataallene Au complex while the Cu acetylide furnishes a CuPPh3+alkynylborate complex with a hydride bridging boron to copper.
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- PAR ID:
- 10674781
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 62
- Issue:
- 4
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 1193 to 1196
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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