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Transition metal pincer complex
In chemistry, a transition metal pincer complex is a type of coordination complex with a pincer ligand. Pincer ligands are chelating agents that binds tightly to three adjacent coplanar sites in a meridional configuration. The inflexibility of the pincer-metal interaction confers high thermal stability to the resulting complexes. This stability is in part ascribed to the constrained geometry of the pincer, which inhibits cyclometallation of the organic substituents on the donor sites at each end. In the absence of this effect, cyclometallation is often a significant deactivation process for complexes, in particular limiting their ability to effect C-H bond activation. The organic substituents also define a hydrophobic pocket around the reactive coordination site. Stoichiometric and catalytic applications of pincer complexes have been studied at an accelerating pace since the mid-1970s. Most pincer ligands contain phosphines. Reactions of metal-pincer complexes are localized at three sites perpendicular to the plane of the pincer ligand, although in some cases one arm is hemi-labile and an additional coordination site is generated transiently. Early examples of pincer ligands (not called such originally) were anionic with a carbanion as the central donor site and flanking phosphine donors; these compounds are referred to as PCP pincers.
Although the most common class of pincer ligands features PCP donor sets, variations have been developed where the phosphines are replaced by thioethers and tertiary amines. Many pincer ligands also feature nitrogenous donors at the central coordinating group position (see figure), such as pyridines.
An easily prepared pincer ligand is POCOP. Many tridentate ligands types occupy three contiguous, coplanar coordination sites. The most famous such ligand is terpyridine (“terpy”). Terpy and its relatives lack the steric bulk of the two terminal donor sites found in traditional pincer ligands.
Metal pincer complexes are often prepared through C-H bond activation.
Ni(II) N,N,N pincer complexes are active in Kumada, Sonogashira, and Suzuki-Miyaura coupling reactions with unactivated alkyl halides.
The pincer ligand is most often an anionic, two-electron donor to the metal centre. It consists of a rigid, planar backbone usually consisting of aryl frameworks and has two neutral, two-electron donor groups at the meta-positions. The general formula for pincer ligands is 2,6-(ER2)2C6H3 – abbreviated ECE – where E is the two-electron donor and C is the ipso-carbon of the aromatic backbone (e.g. PCP – two phosphine donors). Due to the firm tridentate coordination mode, it allows the metal complexes to exhibit high thermal stability as well as air-stability. It also implies that a reduced number of coordination sites are available for reactivity, which often limits the number of undesirable products formed in the reaction due to ligand exchange, as this process is suppressed.
There are various types of pincer ligands that are used in transition metal catalysis. Often, they have the same two-electron donor flanking the metal centre, but this is not a requirement.
The most common pincer ligand designs are PCP, NCN, PCN, SCS, and PNO. Other elements that have been employed at different positions in the ligand are boron, arsenic, silicon, and even selenium.
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Transition metal pincer complex
In chemistry, a transition metal pincer complex is a type of coordination complex with a pincer ligand. Pincer ligands are chelating agents that binds tightly to three adjacent coplanar sites in a meridional configuration. The inflexibility of the pincer-metal interaction confers high thermal stability to the resulting complexes. This stability is in part ascribed to the constrained geometry of the pincer, which inhibits cyclometallation of the organic substituents on the donor sites at each end. In the absence of this effect, cyclometallation is often a significant deactivation process for complexes, in particular limiting their ability to effect C-H bond activation. The organic substituents also define a hydrophobic pocket around the reactive coordination site. Stoichiometric and catalytic applications of pincer complexes have been studied at an accelerating pace since the mid-1970s. Most pincer ligands contain phosphines. Reactions of metal-pincer complexes are localized at three sites perpendicular to the plane of the pincer ligand, although in some cases one arm is hemi-labile and an additional coordination site is generated transiently. Early examples of pincer ligands (not called such originally) were anionic with a carbanion as the central donor site and flanking phosphine donors; these compounds are referred to as PCP pincers.
Although the most common class of pincer ligands features PCP donor sets, variations have been developed where the phosphines are replaced by thioethers and tertiary amines. Many pincer ligands also feature nitrogenous donors at the central coordinating group position (see figure), such as pyridines.
An easily prepared pincer ligand is POCOP. Many tridentate ligands types occupy three contiguous, coplanar coordination sites. The most famous such ligand is terpyridine (“terpy”). Terpy and its relatives lack the steric bulk of the two terminal donor sites found in traditional pincer ligands.
Metal pincer complexes are often prepared through C-H bond activation.
Ni(II) N,N,N pincer complexes are active in Kumada, Sonogashira, and Suzuki-Miyaura coupling reactions with unactivated alkyl halides.
The pincer ligand is most often an anionic, two-electron donor to the metal centre. It consists of a rigid, planar backbone usually consisting of aryl frameworks and has two neutral, two-electron donor groups at the meta-positions. The general formula for pincer ligands is 2,6-(ER2)2C6H3 – abbreviated ECE – where E is the two-electron donor and C is the ipso-carbon of the aromatic backbone (e.g. PCP – two phosphine donors). Due to the firm tridentate coordination mode, it allows the metal complexes to exhibit high thermal stability as well as air-stability. It also implies that a reduced number of coordination sites are available for reactivity, which often limits the number of undesirable products formed in the reaction due to ligand exchange, as this process is suppressed.
There are various types of pincer ligands that are used in transition metal catalysis. Often, they have the same two-electron donor flanking the metal centre, but this is not a requirement.
The most common pincer ligand designs are PCP, NCN, PCN, SCS, and PNO. Other elements that have been employed at different positions in the ligand are boron, arsenic, silicon, and even selenium.