Pincer Ligand (pincer + ligand)

Distribution by Scientific Domains


Selected Abstracts


Oxido Pincer Ligands , Exploring the Coordination Chemistry of Bis(hydroxymethyl)pyridine Ligands for the Late Transition Metals

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2009
Axel Klein
Abstract Coordination of the 2,6-bis(hydroxymethyl)pyridine-based oxido pincer ligands RR,pydimH2 [R = R, = H (pydimH2); R = R, = Me (pydipH2); R = 2-tolyl, R, = Me (pydotH2)] towards late transition metals CoII, NiII, CuII, ZnII, PdII and PtII allows the formation of molecular species (complexes), which exhibit three main structural motifs in the solid state. The two main species are pentacoordinate [(RR,pydimH2)MCl2] and hexacoordinate [(RR,pydimH2)2M]X2, both of which are stable in solution and can be interconverted by changing the solvent polarity. The disproportionation equilibrium [(RR,pydimH2)MCl2] [rlhar2] [(RR,pydimH2)2M]2+ + [MCl4]2, was studied by optical spectroscopy. The chiral ligand pydotH2 allows the formation of chiral complexes. In the square-planar complexes [(pydimH2)2MCl2] (M = PdII or PtII) the oxido donor functions of the ligands do not take part in the coordination.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


Diastereopure Cationic NCN-Pincer Palladium Complexes with Square Planar ,4 - N,C,N,O Coordination

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2006
Silvia Gosiewska
Abstract Neutral NCN-pincer palladium bromide complex 2 containing the monoanionic, enantiopure pincer ligand 2,6-bis{[(S)-2-hydroxymethyl-1-pyrrolidinyl]methyl}phenyl bromide (1) with bis- ortho -(S)-prolinol substituents was synthesized and isolated as a mixture of three stereoisomers [(SN,SN,SC,SC), (RN,SN,SC,SC), and (RN,RN,SC,SC)] in a 1:1:1 ratio. Upon abstraction of the bromide ion from the unresolved mixture of 2, single diastereoisomers of the cationic complexes [3]BF4 and [3]PF6, respectively, were formed with a unique,4 - N,C,N,O coordination mode of ligand 1. X-ray crystal structure determination established the intramolecular,4 - N,C,N,O coordination of 1 to palladium where the typical mer -,3 - N,C,N pincer coordination is accompanied by coordination of one of the hydroxy groups of the (S)-prolinol moieties. The water molecule that was cocrystallized in the crystal structure of [3]PF6 does not coordinate to palladium, but instead is involved in a hydrogen bonding network. The catalytic potential of both cationic complexes, [3]BF4 and [3]PF6, was tested in an aldol reaction of aldehydes with methyl isocyanoacetate to yield the oxazoline products as racemic mixtures.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]


Ruthenium ONO-Type Pincer Complex: Synthesis, Structural Characterization, and Catalysis

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2010
Yao Zhang
Abstract A novel nitrone-based pincer ligand was developed by a single-step synthesis from N -(tert -butyl)hydroxylamine acetate and 2,6-pyridinedicarboxaldehyde. The developed ligand allowed us to synthesize a cationic ruthenium pincer complex. A distorted octahedral coordination environment around the ruthenium center was observed. The complex showed excellent catalytic activity in transfer hydrogenation reactions with turnover numbers up to 590,000. [source]


Efficient Heterogeneous Dual Catalyst Systems for Alkane Metathesis

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2010
Zheng Huang
Abstract A fully heterogeneous and highly efficient dual catalyst system for alkane metathesis (AM) has been developed. The system is comprised of an alumina-supported iridium pincer catalyst for alkane dehydrogenation/olefin hydrogenation and a second heterogeneous olefin metathesis catalyst. The iridium catalysts bear basic functional groups on the aromatic backbone of the pincer ligand and are strongly adsorbed on Lewis acid sites on alumina. The heterogeneous systems exhibit higher lifetimes and productivities relative to the corresponding homogeneous systems as catalyst/catalyst interactions and bimolecular decomposition reactions are inhibited. Additionally, using a "two-pot" device, the supported Ir catalysts and metathesis catalysts can be physically separated and run at different temperatures. This system with isolated catalysts shows very high turnover numbers and is selective for the formation of high molecular weight alkanes. [source]


Highly Active and Recyclable Heterogeneous Iridium Pincer Catalysts for Transfer Dehydrogenation of Alkanes

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009
Zheng Huang
Abstract Pincer-ligated iridium complexes have proven to be highly effective catalysts for the dehydrogenation and transfer-dehydrogenation of alkanes. Immobilization onto a solid support offers significant potential advantages in the application of such catalysts particularly with respect to catalyst separation and recycling. We describe three approaches toward such immobilization: (i) covalent attachment to a Merrifield resin, (ii) covalent bonding to silica via a pendant alkoxysilane group, and (iii) adsorption on ,-alumina (,-Al2O3), through basic functional groups on the para- position of the pincer ligand. The simplest of these approaches, adsorption on ,-Al2O3, is also found to be the most effective, yielding catalysts that are robust, recyclable, and comparable to or even more active than the corresponding species in solution. Spectroscopic evidence (NMR, IR) and studies of catalytic activity support the hypothesis that binding occurs at the para- substituent and that this has only a relatively subtle and indirect influence on catalytic behavior. [source]


Acceptorless Dehydrogenation of Alcohols: Perspectives for Synthesis and H2 Storage.

CHEMCATCHEM, Issue 1 2009
Anja Friedrich
Without acception: Acetals are selectively obtained from acceptorless alcohol dehydrogenation (AAD) of aliphatic primary alcohols catalyzed by a ruthenium complex bearing an acridine-based PNP pincer ligand. This unprecedented reaction represents a new tool for one-step acetal synthesis under mild reaction conditions and demonstrates that AAD selectivity can be controlled by changes to the catalyst ligand sphere. [source]