The elucidation of formation mechanisms is mandatory for understanding and planning of synthetic routes. For (bio-)organic and organometallic compounds, this has long been realized even for very complicated molecules, whereas the formation of ligand-free inorganic molecules has widely remained a black box to date. This is due to poor structural relationships between reactants and products and the lack of structurally related intermediates—due to the comparably high coordination flexibility of involved atoms. Here we report on investigations of the stepwise formation of multimetallic clusters, based on a series of crystal structures and complementary quantum-chemical studies of (Ge2As2)2−, (Ge7As2)2−, [Ta@Ge6As4]3−, [Ta@Ge8As4]3− and [Ta@Ge8As6]3−. The study makes use of efficient quantum-chemical tools, enabling the first detailed screening of the energy hypersurface along the formation of ligand-free inorganic species for a semi-quantitative picture. The results can be generalized for an entire family of multimetallic clusters.
This review article provides a survey of contemporary investigations on main group metal cluster formation, addressing homo- and heterometallic clusters (including small numbers of transition metal atoms), with or without an external ligand shell, thereby excluding clusters with non-metal atoms as bridging ligands. Most of the studies reflected herein represent insights into the formation of intermediates from the starting material, or the final cluster formation from established intermediates. In rare cases, the entire process was suggested as a result of comprehensive, multi-method elucidations. The article is to be understood as a state-of-the-art report, as the subject matter is currently a rising field of research, which is still in its infancy, despite some early activities that date back to the 1980s. At the same time, the article intends to point toward both the importance and the feasibility of according studies, in order to encourage researchers to gain even more knowledge in this field. Only deep understanding of cluster formation will allow for design, and ultimately control, of their syntheses, with the long-term goal of their optimization and purposeful application in catalysis or novel material synthesis.
The novel binary P analogue (GeP) proved to be a suitable precursor for heteroatomic cluster synthesis. Over time in solution, it rearranges to form (GeP), as shown by NMR studies and X-ray diffraction. Reactions of (GeP) with CdPh afford [K(crypt-222)][Cd(GeP)], containing an unprecedented ternary cluster anion with a triangular Cd moiety.
The ligation of a N-heterocyclic carbene (NHC) to group 11 metal salts (Cu, Ag) was explored as an alternative to PR(3) ligands for the formation of copper- and silver-chalcogenolate cluster complexes. AgOAc and CuCl salts ligate with the NHC 1,3-di-isopropylbenzimidazole-2-ylidene ((i)Pr(2)-bimy) forming [Ag(OAc)((i)Pr(2)-bimy)] 1, [Ag(OAc)((i)Pr(2)-bimy)(2)] 2, [CuCl((i)Pr(2)-bimy)](2)3 and [CuCl((i)Pr(2)-bimy)(2)] 4 depending on the ratio of ligand to metal used. These have been characterized via spectroscopic and crystallographic methods. Complexes 1 and 3 were reacted with S(Ph)SiMe(3) and Se(Ph)SiMe(3) to form the polynuclear metal-chalcogenolates [Ag(4)(μ-EPh)(4)((i)Pr(2)-bimy)(4)] (5, E = S; 6, E = Se) and [Cu(3)(μ-EPh)(3)((i)Pr(2)-bimy)(3)] (7, E = S; 8, E = Se) in good yields. The structures of 5-8, as determined by single crystal X-ray crystallography, are described.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.