Diantimony Complexes [Cp2RMo2(CO)4(μ,η2-Sb2)] (CpR=C5H5, C5H4tBu) as Unexpected Ligands Stabilizing Silver(I)n (n=1-4) Monomers, Dimers and Chains

Synthesis and reactivity of transition metal compounds bearing naked pnictogen atoms is an active research area with remarkable bonding patterns observed in the formed compounds. Within this field, intense investigations on the coordination behavior of complexes possessing P-n and As-n (2 <= n <= 5) moieties have been conducted. However, studies on heavier analogues have been ignored so far due to arduous challenges related to low yields and moderate air stability. Herein, we present the first in-depth study addressing the reactivity of organometallic complexes containing Sb-donor atoms with several Ag-I salts. These reactions afforded twelve unprecedented aggregates as monomers, dimers as well as three- and four-membered chains of Ag-I ions claimed in the literature to be inaccessible. Interatomic distances as well as computational evidence obtained with help of several different methods suggest the presence of Ag center dot center dot center dot Ag interactions in all complexes containing more than one Ag-I ion.

Automated summary

Synthesis and reactivity of transition metal compounds with naked pnictogen atoms have been actively studied, revealing interesting bonding patterns in the formed compounds. While coordination behavior of complexes with P-n and As-n (2 <= n <= 5) groups has been extensively investigated, studies on heavier analogues have been overlooked due to challenges in yields and air stability. In this work, we report the first comprehensive study on the reactivity of organometallic complexes containing Sb-donor atoms with various Ag-I salts, leading to the formation of unprecedented aggregates including monomers, dimers, and chains of Ag-I ions that were previously considered inaccessible. Computational evidence and interatomic distances suggest the presence of Ag···Ag interactions in complexes with multiple Ag-I ions.