RT info:eu-repo/semantics/article
T1 Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals
A1 García Romero, Álvaro
A1 Waters, Jessica E.
A1 Jethwa, Rajesh B.
A1 Bond, Andrew D.
A1 Colebatch, Annie Louise
A1 García Rodríguez, Raúl
A1 Wright, Dominic Simon
K1 Química inorgánica
K1 Coinage Metals
K1 Metales de coincidencia
K1 2303 Química Inorgánica
AB 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.
PB American Chemical Society
SN 0020-1669
YR 2023
FD 2023
LK https://uvadoc.uva.es/handle/10324/59798
UL https://uvadoc.uva.es/handle/10324/59798
LA eng
NO Inorganic Chemistry,  2023, 62, 11, 4625–4636
NO Producción Científica
DS UVaDOC
RD 23-dic-2024