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A unique four‐coordinate, classical gold(I)‐carbonyl complex with substantial backdonation from gold has been isolated by using a B‐methylated and fluorinated tris(pyridyl)borate chelator. Its lighter silver(I) and copper(I) analogs enabled a study of trends in the coinage‐metal family. The B‐arylated ligand version also afforded a gold–carbon monoxide complex that displays a notably low C−O stretch value, but with trigonal planar geometry at the gold. A computational analysis shows that the Au^I−CO bonds of these tris(pyridyl)borate ligand‐supported molecules consist of electrostatic attraction, OC→Au σ‐donation, and very significant Au→CO π‐back‐bonding components. The latter is responsible for the observed C−O stretching frequencies, which are lower than in free CO.

 

A useful ligand involving three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized in coinage metal chemistry. This tris(pyridyl)borate serves as an excellent ligand support for the stabilization of ethylene complexes of copper, silver and gold. 

Ethylene complexes of gold( i ) have been stabilized by electron-rich, κ 2 -bound tris(pyrazolyl)borate ligands. Large up-field shifts of olefinic carbon NMR resonances and relatively long CC distances of gold bound ethylene are indicative of significant Au( i ) → ethylene π-backbonding relative to the analog supported by a weakly donating ligand, consistent with the computational data. 

Following an ongoing interest in the study of transition metal complexes with exotic bonding networks, we report herein the synthesis of a family of heterobimetallic triangular clusters involving Ru and Pd atoms. These are the first examples of trinuclear complexes combining these nuclei. Structural and bonding analyses revealed both analogies and unexpected differences for these [Pd 2 Ru] + complexes compared to their parent [Pd 3 ] + peers. Noticeably, participation of the Ru atom in the π-aromaticity of the coordinated benzene ring makes the synthesized compound the second reported example of ‘bottled’ double aromaticity. This can also be referred to as spiroaromaticity due to the participation of Ru in two aromatic systems at a time. Moreover, the [Pd 2 Ru] + kernel exhibits unprecedented orbital overlap of Ru d z2 AO and two Pd d xy or d x2−y2 AOs. The present findings reveal the possibility of synthesizing stable clusters with delocalized metal–metal bonding from the combination of non-adjacent elements of the periodic table which has not been reported previously. 

Abstract Sandwich-type clusters with the planar fragment containing a heterometallic sheet have remained elusive. In this work, we introduce the [K(2,2,2-crypt)] 4 {(Ge 9 ) 2 [ η 6 -Ge(PdPPh 3 ) 3 ]} complex that contains a heterometallic sandwich fragment. The title compound is structurally characterized by means of single-crystal X-ray diffraction, which reveals the presence of an unusual heteroatomic metal planar fragment Ge@Pd 3 . The planar fragment contains a rare formal zerovalent germanium core and a peculiar bonding mode of sp 2 -Ge@(PdPPh 3 ) 3 trigonal planar structure, whereas the nonagermanide fragments act as capping ligands. The chemical bonding pattern of the planar fragment consists of three 2c-2e Pd-Ge σ-bonds attaching Pd atoms to the core Ge atom, while the binding between the planar fragment and the aromatic Ge 9 ligands is provided by six 2c-2e Pd-Ge σ-bonds and two delocalized 4c-2e σ-bonds. The synthesized cluster represents a rare example of a sandwich compound with the heteroatomic metal planar fragment and inorganic aromatic capping ligands. 

The most characteristic feature of planar π-aromatics is the ability to sustain a long-range shielding cone under a magnetic field oriented in a specific direction. In this article, we showed that similar magnetic responses can be found in σ-aromatic and spherical aromatic systems. For [Au 13 ] 5+ , long-range characteristics of the induced magnetic field in the bare icosahedral core are revealed, which are also found in the ligand protected [Au 25 (SH) 18 ] − model, proving its spherical aromatic properties, also supported by the AdNDP analysis. Such properties are given by the 8-ve of the structural core satisfying the Hirsch 2( N + 1) 2 rule, which is also found in the isoelectronic [M@Au 12 ] 4+ core, a part of the [MAu 24 (SR) 18 ] 2− (M = Pd, Pt) cluster. This contrasts with the [M@Au 12 ] 6+ core in [MAu 24 (SR) 18 ] 0 (M = Pd, Pt), representing 6-ve superatoms, which exhibit characteristics of planar σ-aromatics. Our results support the spherical aromatic character of stable superatoms, whereas the 6-ve intermediate electron counts satisfy the 4 N + 2 rule (applicable for both π- and σ-aromatics), showing the reversable and controlled interplay between 3D spherical and 2D σ-aromatic clusters.