Synthesis and structural characterisation of the palladium N-heterocyclic carbene cluster complexes [Pd3(μ-CO)3(NHC)3] and [Pd3(μ-SO2)3(NHC)3]

Ellul, Charles E.; Mahon, Mary F.; Whittlesey, Michael K.

doi:10.1016/j.jorganchem.2009.09.018

Cited by 16 publications

(5 citation statements)

References 45 publications

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“…6 consists of a Pt 3 triangle bonded to three μ-CO, one terminal CO, and two IPr ligands (Figure and Table ). Its structure is closely related to previously reported Pt 3 L 3 (μ-CO) 3 clusters , as well as [Pd 3 (CO) 3 (IMes) 3 ] and Pt 2 Ru(CO) 6 (IMes) 2 . The IR spectrum of 6 recorded in a CH 2 Cl 2 solution displays ν(CO) bands attributable to t-CO (2013 cm –1 ) and μ-CO (1823 and 1792 cm –1 ) ligands.…”

Section: Resultssupporting

confidence: 86%

“…The formation of 8 is likely to proceed through an associative mechanism with the formation of a [Pt 3 (CO) 4 (IPr) 3 ] intermediate followed by CO elimination. Indeed, both related [Pt 3 (CO) 3 (PR 3 ) 3 ] and [Pt 3 (CO) 3 (PR 3 ) 4 ] derivatives were previously described. − ,− ,, The molecular structure of 8 (Figure and Table ) is reminiscent of those previously reported for the phosphine derivatives [Pt 3 (CO) 3 (PR 3 ) 3 ] and the palladium analogue [Pd 3 (CO) 3 (IMes) 3 ]. ,, …”

Section: Resultsmentioning

confidence: 57%

“…N-Heterocyclic carbenes (NHCs) are nowadays widely employed as ligands in inorganic, organometallic, and coordination chemistry and catalysis. − Recently, their use for the stabilization of NPs and ultrasmall NPs has been investigated. − In contrast, examples of molecular clusters containing NHC ligands are more scarce, and systematic studies have mainly been focused on ruthenium and osmium clusters. − The inclusion of NHC ligands in the coordination sphere of carbonyl clusters of other transition metals and the use of higher nuclearity clusters and heterometallic clusters are some exciting aspects of this chemistry that have started to be investigated in the very recent years. ,− A general approach for the synthesis of heterometallic CO/NHC clusters might be represented by the reaction of preformed metal carbonyl clusters with M(NHC)X complexes (M = Cu, Ag, Au; X = Cl, Ph), as was recently described in a few papers. − …”

Section: Introductionmentioning

confidence: 99%

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Reactions of Platinum Carbonyl Chini Clusters with Ag(NHC)Cl Complexes: Formation of Acid–Base Lewis Adducts and Heteroleptic Clusters

et al. 2017

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The reactions of anionic platinum carbonyl Chini clusters [Pt(CO)] [n = 2 (1), 3 (2), 4 (3)] with Ag(IPr)Cl [IPr = CNH(CHPr)] afford the neutral acid-base Lewis adducts [Pt(CO)(AgIPr)] (4) and [Pt(CO)(AgIPr)] (5). These are thermally transformed into the homometallic heteroleptic neutral cluster [Pt(CO)(IPr)] (6). Alternatively, 6 can be obtained from the reactions of 1-3 with an excess of the free IPr carbene ligand. The formation of 6 is sometimes accompanied by trace amounts of [Pt(CO)(IPr)] (7). The reaction of 6 with free IPr affords the closely related [Pt(CO)(IPr)] (8) heteroleptic cluster by substitution of the unique terminal CO ligand with a third IPr ligand. The reactions of 1-3 with Ag(IMes)Cl [IMes = CNH(CHMe)] proceed differently from those involving Ag(IPr)Cl. Indeed, the only product isolated after workup is the bimetallic tetranuclear cluster [Pt(CO)(IMes)(AgCl)] (9). 9 slowly reacts under a CO atmosphere, resulting in the pentanuclear [Pt(CO)(IMes)] (10) complex. All of the new clusters 4-10 have been spectroscopically characterized and their molecular structures determined by X-ray crystallography. 4 and 5 retain the original trigonal-prismatic structures of the parent anionic Chini clusters, which are capped by two [Ag(IPr)] moieties. Conversely, 6-9 are based on a Pt triangular core decorated by CO and N-heterocyclic carbene ligands as well as Pt(CO) (in the case of 7) and AgCl (9) moieties. 10 displays an edge-bridged tetrahedral geometry.

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Section: Resultssupporting

confidence: 86%

Section: Resultsmentioning

confidence: 57%

Section: Introductionmentioning

confidence: 99%

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Reactions of Platinum Carbonyl Chini Clusters with Ag(NHC)Cl Complexes: Formation of Acid–Base Lewis Adducts and Heteroleptic Clusters

et al. 2017

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“…Whittlesey and co‐workers used potassium graphite to react with Pd(II) complexes in the presence of CO, and afforded the neutral [Pd 3 ( μ ‐CO) 3 (NHC) 3 ] cluster. [ 26 ] Then putting it under a SO 2 atmosphere would synthesize structure [Pd 3 ( μ ‐SO 2 ) 3 (NHC) 3 ]. Compared to similar triangular clusters with phosphine ligands, more rigid NHC ligand is beneficial for the stability.…”

Section: Synthesis and Structures Of Pd Clustersmentioning

confidence: 99%

Low Valent Palladium Clusters: Synthesis, Structures and Catalytic Applications

Liu

Zhao²

2020

Chin. J. Chem.

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As one of the most common transition metal catalysts, mononuclear palladium catalysts have been developed systematically and a widely recognized catalytic mechanism featured with a Pd 0 /Pd II catalytic cycle for a palladium center has been proposed. However, recent research works have revealed that palladium clusters may also be catalysts or catalytic intermediates involved in the catalytic processes. This major discovery brings new perspectives for a deep and comprehensive understanding of the Pd-catalyzed reaction mechanisms. Combining with the latest advances in the field of organometallic chemistry, we here highlight the synthesis, structures, and catalytic reactivities of palladium cluster compounds. This review discusses several well-defined synthetic strategies and diverse palladium cluster-based catalytic systems in detail, to provide insights into the rational design of promising palladium cluster catalysts and the effective search for appropriate synthetic methods. Qian Liu (left) was born in 1997 in Hebei, China. She gained her Bachelor degree from School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, in 2019. She is now pursuing her Ph.D. degree at Tsinghua University under the supervision of Dr. Liang Zhao. Her current research focuses on the synthesis and catalytic applications of palladium clusters. Liang Zhao (right) was born in 1981 in Ningxia, China. He obtained his Bachelor degree at Peking University (2002) and a Ph.D. degree at Chemistry Department of the Chinese University of Hong Kong under the guidance of Prof. Thomas C. W. Mak (2007). Subsequently, he joined Prof. Peter J. Stang's group at the University of Utah as a Postdoctoral fellow. In November 2009, he joined Chemistry Department at Tsinghua University. His research spans the interdisciplinary areas of supramolecular chemistry and organometallic chemistry, mostly focusing on the controllable synthesis and reactivity studies of polynuclear organometallic clusters.

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“…The formation of trinuclear and multinuclear complexes is also a possible option. They can act as intermediates, represent resting states, or block the catalytic cycle by generating stable nonreactive species. − …”

Section: Introductionmentioning

confidence: 99%

Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolation

et al. 2023

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A common assumption that dimeric metal complexes in many catalytic systems represent a resting state and are not directly involved in catalytic processes was revised in a combined experimental and theoretical study. On-cycle participation of dimeric metal complexes, rather than typically assumed off-cycle involvement, was revealed, and advantageous performance in terms of improved selectivity was observed. The conceptual rationalization for the participation of dimeric species in the catalytic cycle was developed. The Pd-catalyzed hydrothiolation process (where strong Pd−S binding is well established and a persistent opinion for the inactive/poisoning role of dimeric species is presumed) was evaluated as a challenging system to test the concept. Activation of an (NHC)Pd(Cl)(acac) precatalyst (NHC�N-heterocyclic carbene and acac�acetylacetonate) under the reaction conditions produced monomeric (NHC)Pd(SPh) 2 or dimeric (NHC) 2 Pd 2 (SPh) 4 species depending on the steric bulkiness of the NHC ligand. Dimeric complexes possessed higher selectivity and tolerated disulfide impurities in contrast to monomeric complexes. Quantum chemical modeling suggested that dimeric catalysis proceeds through the opening of only one (μ-SPh)−Pd bridging bond with retention of the dimeric structure. The second bridging bond is maintained, which prevents the monomerization of the complex. Catalytically active species were detected in a hydrothiolation reaction by high-resolution mass spectrometry and NMR spectroscopy. Proving the opportunity for productive homogeneous catalysis via strongly coordinated dimeric metal species opens new opportunities for catalyst design in the increased nuclearity dimension.

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Synthesis and structural characterisation of the palladium N-heterocyclic carbene cluster complexes [Pd3(μ-CO)3(NHC)3] and [Pd3(μ-SO2)3(NHC)3]

Cited by 16 publications

References 45 publications

Reactions of Platinum Carbonyl Chini Clusters with Ag(NHC)Cl Complexes: Formation of Acid–Base Lewis Adducts and Heteroleptic Clusters

Reactions of Platinum Carbonyl Chini Clusters with Ag(NHC)Cl Complexes: Formation of Acid–Base Lewis Adducts and Heteroleptic Clusters

Low Valent Palladium Clusters: Synthesis, Structures and Catalytic Applications

Expanding the Role of Dimeric Species: On-Cycle Involvement, Improved Stability, and Control of Stereo-Specificity. A Case Study of Atom-Economic Catalytic Hydrothiolation

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