---
_id: '12737'
abstract:
- lang: eng
text: The substitution of heavier, more metallic atoms into classical organic ligand
frameworks provides an important strategy for tuning ligand properties, such as
ligand bite and donor character, and is the basis for the emerging area of main-group
supramolecular chemistry. In this paper, we explore two new ligands [E(2-Me-8-qy)3]
[E = Sb (1), Bi (2); qy = quinolyl], allowing a fundamental comparison of their
coordination behavior with classical tris(2-pyridyl) ligands of the type [E′(2-py)3]
(E = a range of bridgehead atoms and groups, py = pyridyl). A range of new coordination
modes to Cu+, Ag+, and Au+ is seen for 1 and 2, in the absence of steric constraints
at the bridgehead and with their more remote N-donor atoms. A particular feature
is the adaptive nature of these new ligands, with the ability to adjust coordination
mode in response to the hard–soft character of coordinated metal ions, influenced
also by the character of the bridgehead atom (Sb or Bi). These features can be
seen in a comparison between [Cu2{Sb(2-Me-8-qy)3}2](PF6)2 (1·CuPF6) and [Cu{Bi(2-Me-8-qy)3}](PF6)
(2·CuPF6), the first containing a dimeric cation in which 1 adopts an unprecedented
intramolecular N,N,Sb-coordination mode while in the second, 2 adopts an unusual
N,N,(π-)C coordination mode. In contrast, the previously reported analogous ligands
[E(6-Me-2-py)3] (E = Sb, Bi; 2-py = 2-pyridyl) show a tris-chelating mode in their
complexes with CuPF6, which is typical for the extensive tris(2-pyridyl) family
with a range of metals. The greater polarity of the Bi–C bond in 2 results in
ligand transfer reactions with Au(I). Although this reactivity is not in itself
unusual, the characterization of several products by single-crystal X-ray diffraction
provides snapshots of the ligand transfer reaction involved, with one of the products
(the bimetallic complex [(BiCl){ClAu2(2-Me-8-qy)3}] (8)) containing a Au2Bi core
in which the shortest Au → Bi donor–acceptor bond to date is observed.
acknowledgement: The authors thank the Walters-Kundert Studentship of Selwyn College
(scholarship for J.E.W.), the Leverhulme Trust (R.G.-R. and D.S.W., grant RPG-2017-146),
the Australian Research Council (A.L.C., DE200100450), the Spanish Ministry of Science
and Innovation (MCI) and the Spanish Ministry of Science, Innovation and Universities
(MCIU) (R.G.-R., PID2021-124691NB-I00, funded by MCIN/AEI/10.13039/501100011033/FEDER,
UE and PGC2018-096880-A-I00, MCIU/AEI/FEDER), The University of Valladolid and Santander
Bank (Fellowship for A.G.-R.), and the U.K. EPSRC and The Royal Dutch Shell plc.
(I-Case award for R.B.J., EP/R511870/1) for financial support. Calculations were
carried out on an in-house Odyssey HPC cluster (Cambridge), and the authors are
grateful for the calculation time used.
article_processing_charge: No
article_type: original
author:
- first_name: Álvaro
full_name: García-Romero, Álvaro
last_name: García-Romero
- first_name: Jessica E.
full_name: Waters, Jessica E.
last_name: Waters
- first_name: Rajesh B
full_name: Jethwa, Rajesh B
id: 4cc538d5-803f-11ed-ab7e-8139573aad8f
last_name: Jethwa
orcid: 0000-0002-0404-4356
- first_name: Andrew D.
full_name: Bond, Andrew D.
last_name: Bond
- first_name: Annie L.
full_name: Colebatch, Annie L.
last_name: Colebatch
- first_name: Raúl
full_name: García-Rodríguez, Raúl
last_name: García-Rodríguez
- first_name: Dominic S.
full_name: Wright, Dominic S.
last_name: Wright
citation:
ama: García-Romero Á, Waters JE, Jethwa RB, et al. Highly adaptive nature of group
15 tris(quinolyl) ligands─studies with coinage metals. Inorganic Chemistry.
2023;62(11):4625-4636. doi:10.1021/acs.inorgchem.3c00057
apa: García-Romero, Á., Waters, J. E., Jethwa, R. B., Bond, A. D., Colebatch, A.
L., García-Rodríguez, R., & Wright, D. S. (2023). Highly adaptive nature of
group 15 tris(quinolyl) ligands─studies with coinage metals. Inorganic Chemistry.
American Chemical Society. https://doi.org/10.1021/acs.inorgchem.3c00057
chicago: García-Romero, Álvaro, Jessica E. Waters, Rajesh B Jethwa, Andrew D. Bond,
Annie L. Colebatch, Raúl García-Rodríguez, and Dominic S. Wright. “Highly Adaptive
Nature of Group 15 Tris(Quinolyl) Ligands─studies with Coinage Metals.” Inorganic
Chemistry. American Chemical Society, 2023. https://doi.org/10.1021/acs.inorgchem.3c00057.
ieee: Á. García-Romero et al., “Highly adaptive nature of group 15 tris(quinolyl)
ligands─studies with coinage metals,” Inorganic Chemistry, vol. 62, no.
11. American Chemical Society, pp. 4625–4636, 2023.
ista: García-Romero Á, Waters JE, Jethwa RB, Bond AD, Colebatch AL, García-Rodríguez
R, Wright DS. 2023. Highly adaptive nature of group 15 tris(quinolyl) ligands─studies
with coinage metals. Inorganic Chemistry. 62(11), 4625–4636.
mla: García-Romero, Álvaro, et al. “Highly Adaptive Nature of Group 15 Tris(Quinolyl)
Ligands─studies with Coinage Metals.” Inorganic Chemistry, vol. 62, no.
11, American Chemical Society, 2023, pp. 4625–36, doi:10.1021/acs.inorgchem.3c00057.
short: Á. García-Romero, J.E. Waters, R.B. Jethwa, A.D. Bond, A.L. Colebatch, R.
García-Rodríguez, D.S. Wright, Inorganic Chemistry 62 (2023) 4625–4636.
date_created: 2023-03-19T23:00:59Z
date_published: 2023-03-08T00:00:00Z
date_updated: 2023-08-01T13:42:59Z
day: '08'
department:
- _id: StFr
doi: 10.1021/acs.inorgchem.3c00057
external_id:
isi:
- '000956110300001'
pmid:
- '36883367'
intvolume: ' 62'
isi: 1
issue: '11'
language:
- iso: eng
month: '03'
oa_version: None
page: 4625-4636
pmid: 1
publication: Inorganic Chemistry
publication_identifier:
eissn:
- 1520-510X
issn:
- 0020-1669
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Highly adaptive nature of group 15 tris(quinolyl) ligands─studies with coinage
metals
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 62
year: '2023'
...