Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)‐Cyclobutadiene Complex

Angewandte Chemie International Edition, vol. 61, pp. e202202019

Abstract

Abstract Understanding the bonding of gold(I) species has been central to the development of gold(I) catalysis. Herein, we present the synthesis and characterization of the first gold(I)‐cyclobutadiene complex, accompanied with bonding analysis by state‐of‐the‐art energy decomposition analysis methods. Analysis of possible coordination modes for the new species not only confirms established characteristics of gold(I) bonding, but also suggests that Pauli repulsion is a key yet hitherto overlooked element. Additionally, we obtain a new perspective on gold(I)‐bonding by comparison of the gold(I)‐cyclobutadiene to congeners stabilized by p‐, d‐, and f‐block metals. Consequently, we refine the gold(I) bonding model, with a delicate interplay of Pauli repulsion and charge transfer as the key driving force for various coordination motifs. Pauli repulsion is similarly determined as a significant interaction in AuI‐alkyne species, corroborating this revised understanding of AuI bonding.

Authors 5

1. Zeng Rong Wong

   University of California, Berkeley

   Affiliation as printed

   Department of Chemistry University of California, Berkeley 420 Latimer Hall Berkeley CA 94720 USA

   Department of Chemistry, University of California, Berkeley, 420 Latimer Hall, Berkeley, CA 94720 USA

   These authors contributed equally to this work. Names are sorted reverse alphabetically

2. Tim K. Schramm Aachen Department of Chemistry

   RWTH Aachen University · University of California, Berkeley

   Affiliation as printed

   Department of Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany

   Department of Chemistry University of California, Berkeley 420 Latimer Hall Berkeley CA 94720 USA

   Department of Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany

   Department of Chemistry, University of California, Berkeley, 420 Latimer Hall, Berkeley, CA 94720 USA

   These authors contributed equally to this work. Names are sorted reverse alphabetically

3. Matthias Loipersberger

   University of California, Berkeley

   Affiliation as printed

   Department of Chemistry University of California, Berkeley 420 Latimer Hall Berkeley CA 94720 USA

   Department of Chemistry, University of California, Berkeley, 420 Latimer Hall, Berkeley, CA 94720 USA

   These authors contributed equally to this work. Names are sorted reverse alphabetically

4. Martin Head‐Gordon corresponding

   Lawrence Berkeley National Laboratory · University of California, Berkeley

   Affiliation as printed

   Chemical Sciences Division Lawrence Berkeley National Laboratory One Cyclotron Road, MS 70A3307 Berkeley CA 94720 USA

   Department of Chemistry University of California, Berkeley 420 Latimer Hall Berkeley CA 94720 USA

   Chemical Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, MS 70A3307, Berkeley, CA 94720 USA

   Department of Chemistry, University of California, Berkeley, 420 Latimer Hall, Berkeley, CA 94720 USA

5. F. Dean Toste corresponding

   Lawrence Berkeley National Laboratory · University of California, Berkeley

   Affiliation as printed

   Chemical Sciences Division Lawrence Berkeley National Laboratory One Cyclotron Road, MS 70A3307 Berkeley CA 94720 USA

   Department of Chemistry University of California, Berkeley 420 Latimer Hall Berkeley CA 94720 USA

   Chemical Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, MS 70A3307, Berkeley, CA 94720 USA

   Department of Chemistry, University of California, Berkeley, 420 Latimer Hall, Berkeley, CA 94720 USA