Late Transition Metal Complexes with Pincer Ligands that Comprise N-Heterocyclic Carbene Donor Sites

Farrell, Kevin; Albrecht, Martin

doi:10.1007/3418_2015_127

Cited by 22 publications

(8 citation statements)

References 191 publications

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“…a κ 3 - L,E,L coordination mode), is notorious for its ability to furnish highly stable transition-metal-based catalysts (Figure ). As a result pincer-type complexes have been the focus of intense investigation over many years . There have been a wealth of derivatives featuring a diverse range of donor atoms including phosphorus, nitrogen, sulfur, oxygen, carbon, and others in various combinations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Platinum and Palladium Complexes Featuring a Rare Secondary Borane Pincer Motif

et al. 2018

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The synthesis and characterization of a series of platinum and palladium complexes containing a secondary borane Z-class ligand supported by 2-mercaptopyridine heterocycles is reported herein. Addition of two equivalents of Na[H2B(mp)2] to [Pt(μ-Cl)(COE OMe)]2 (where COE OMe = 8methoxycyclooct-4-en-1-ide) in the presence of two equivalents of a tertiary phosphine {PR3 = PPh3, PCy3, PCyp3, P(o-tol)3, PPh2(o-tol) and PPh2(2-(3-methyl)indolyl)} leads to the formation of the complexes [Pt{κ 3-S,B,S-HB(mp)2}(PR3)] (1-6). Addition of two equivalents of Na[H2B(mp)2] to [Pd(μ-Cl)(COE OMe)]2 in the presence of two equivalents of a tertiary phosphine {PR3 = PPh3, PCy3, PCyp3, and PPh2(o-tol)} leads to the formation of the complexes [Pd{κ 3-S,B,S-HB(mp)2}(PR3)] (7-10). It was also demonstrated that the synthesis of the palladium complex 7 could be achieved from the palladium precursor, [PdCl(Me)(COD)] (where COD = 1,5cyclooctadiene) as an alternative synthetic strategy. In the above reactions, either the COE OMe 2 fragment or the methyl fragment serve to act as a "hydride acceptor" facilitating the ultimate transformation of the borohydride based ligand, [H2B(mp)2]to the corresponding secondary borane  3-S,B,S coordinated HB(mp)2 pincer ligand. The complexes [Pd{κ 3-S,B,S-HB(mp)2}(PR3)] and [Pt{κ 3-S,B,S-HB(mp)2}(PR3)] are rare examples of metal-borane complexes where one hydrogen substituent remains at the boron center. These compounds have particularly short palladium-and platinum-boron distances, the shortest of the structurally characterized compounds being 2.067(6) Å for [Pd{κ 3-S,B,S-HB(mp)2}(PPh2(o-tol))] and 2.076(10) Å, for [Pt{κ 3-S,B,S-HB(mp)2}(PCy3)], respectively (the shorter distances of two independent complexes in the unit cells of both structures).

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Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Platinum and Palladium Complexes Featuring a Rare Secondary Borane Pincer Motif

et al. 2018

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“…The prominence of palladium(II) pincer complexes over their platinum(II) analogues is given by the fact that Pt(II) is one of the most kinetically inert metal ions known, making a double carboplatination more challenging than a single one, as observed for the C^N, C^N^N or C^N^S systems 94 .…”

Section: C^n^c Complexesmentioning

confidence: 99%

Cyclometalated Complexes of Platinum and Gold with Biological Properties: State-of-the-Art and Future Perspectives

Jürgens

Kühn

Casini

2018

CMC

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“…From the wide variety of available ligand architectures, pincer-type ligands have contributed tremendously to the development of earth-abundant metal catalysis. 8 The most commonly encountered structural motifs within this set of ligands are those featuring an XNX (X = NR, PR 2 , P(OR) 2 ) pincer type geometry with a central amino or pyridine donor. 8 In contrast, earth-abundant metal pincer complexes presenting a carbene as central donor are virtually absent from the literature, 9 in particular those containing a PC NHC P type geometry ( Figure 1 ).…”

Section: Introductionmentioning

confidence: 99%

“… 8 The most commonly encountered structural motifs within this set of ligands are those featuring an XNX (X = NR, PR 2 , P(OR) 2 ) pincer type geometry with a central amino or pyridine donor. 8 In contrast, earth-abundant metal pincer complexes presenting a carbene as central donor are virtually absent from the literature, 9 in particular those containing a PC NHC P type geometry ( Figure 1 ). 10 Their absence is quite surprising as carbenes often impart distinct electronic and steric properties to the metal center.…”

Section: Introductionmentioning

confidence: 99%

“…From the wide variety of available ligand architectures, pincer-type ligands have contributed tremendously to the development of earth-abundant metal catalysis . The most commonly encountered structural motifs within this set of ligands are those featuring an XNX (X = NR, PR 2 , P(OR) 2 ) pincer type geometry with a central amino or pyridine donor .…”

Section: Introductionmentioning

confidence: 99%

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Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex

et al. 2020

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Earth-abundant metal pincer complexes have played an important role in homogeneous catalysis during the last ten years. Yet, despite intense research efforts, the synthesis of iron PC carbene P pincer complexes has so far remained elusive. Here we report the synthesis of the first PC NHC P functionalized iron complex [(PC NHC P)FeCl 2 ] ( 1 ) and the reactivity of the corresponding trans -dihydride iron(II) dinitrogen complex [(PC NHC P)Fe(H) 2 N 2 )] ( 2 ). Complex 2 is stable under an atmosphere of N 2 and is highly active for hydrogen isotope exchange at (hetero)aromatic hydrocarbons under mild conditions (50 °C, N 2 ). With benzene- d 6 as the deuterium source, easily reducible functional groups such as esters and amides are well tolerated, contributing to the overall wide substrate scope (e.g., halides, ethers, and amines). DFT studies suggest a complex assisted σ-bond metathesis pathway for C(sp 2 )–H bond activation, which is further discussed in this study.

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Late Transition Metal Complexes with Pincer Ligands that Comprise N-Heterocyclic Carbene Donor Sites

Cited by 22 publications

References 191 publications

Synthesis and Characterization of Platinum and Palladium Complexes Featuring a Rare Secondary Borane Pincer Motif

Synthesis and Characterization of Platinum and Palladium Complexes Featuring a Rare Secondary Borane Pincer Motif

Cyclometalated Complexes of Platinum and Gold with Biological Properties: State-of-the-Art and Future Perspectives

Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex

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