f‐Element–Metal Bonding and the Use of the Bond Polarity To Build Molecular Intermetalloids

Abstract

Metal-metal bonding in heterobimetallic complexes is of fundamental interest due to its implications to both bonding theory and new reactivities. In this Concept, structurally authenticated molecular compounds with direct bonds between rare-earth metals or actinoids and transition or main group metals are summarized. Special attention is given to the use of bond polarity as a tool for designing molecular intermetalloids incorporating rare-earth atoms and transition metals.

Rare‐Earth Metal Oxo/Hydroxo Clusters – Synthesis, Structures, and Applications

“…On the other hand, metal-tometal bonds between the lanthanides and main-group or transition metals have been intensively investigated in the last ten years. [15][16][17] Moreover, in rare-earth chemistry the metal cations favor high coordination numbers (8-12 most common) and have no strict preferences in coordination geometry. [3] To stabilize a cluster core consisting of rare-earth metal cations the presence of Lewis-basic ligands is beneficial but not needed in all cases.…”

Bi- and trimetallic rare-earth–palladium complexes ligated by phosphinoamides

“…1 The application of heterobimetallic complexes in catalysis has been reviewed recently. 3 Examples include complexes with Lu-Ru, 4 Ln-Re (Ln = La, Sm, Yb, Lu), 5 Nd-Fe, 6 and Yb-Fe bonds. For the rare-earth elements only a few complexes with non-supported metal-to-metal bonds to a transition metal are known.…”

“…Kempe et al reported a few Nd-Rh and Nd-Pd complexes about 15 years ago. Co-Ti, 11 Co-Zr, 10,12 Co-Hf, 3 Pt-Zr, 13 V-Fe, 14 Nb-Co, 5b Ta-Co, 5b and Co-U. Hou et al recently published rare-earth-platinum heterobinuclear half-sandwich rare-earthmetal alkyl complexes bearing Cp ligands with a phosphine side arm.…”

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

“…Although the first structurally characterized lanthanide-transition metal bonds were reported in the early 1990s, ([(MeCN)3YbFe(CO)4]2·MeCN)∞ (Deng and Shore, 1991) and Cp2Lu(THF)-RuCp(CO)2 (Beletskaya et al, 1993), the field started developing at a fast pace only in the last decade Butovskii et al, 2010;Liddle and Mills, 2009;Minasian et al, 2009;Oelkers et al, 2012), spurred by Kempe's report of [O(SiMe2N-2-C5H3N-4-Me)2]2NdRh( 2 -C2H4) and…”