Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand

Weisman, Alexander; Gozin, Michael; Kraatz, Heinz‐Bernhard; Milstein, David

doi:10.1021/ic951131h

Cited by 61 publications

(45 citation statements)

References 38 publications

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“…113 Formally, this reaction corresponds to a pyridine tautomerization involving a 1,4-migration of the proton. UV-vis spectrosopic comparison of the pyridylidene complex 160 and the deprotonated pyridyl complex 161 indicates that protonation induces a 16-nm hypsochromic shift of the relevant absorption band in the visible region.…”

Section: Scheme 49mentioning

confidence: 99%

Beyond ConventionalN-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization

et al. 2009

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theme are found via the replacement or displacement of one N atom, thus providing carbenes derived from pyrazolium, isothiazolium, and even quinolinium salts that contain a stabilizing heteroatom in a remote position (G-J in Figure 1). Recently, carbenes such as K, which are comprised of only one heteroatom and lack delocalization through the heterocycle, have been discovered as versatile ligands, thus constituting another important class of carbenes with low heteroatom stabilization. Both the synthesis of the organometallic complexes of these ligands as well as the (catalytic) properties of the coordinated metal centers generally show distinct differences, compared to the more classical NHC complexes, such as C2-metallated imidazolylidenes. This review intends to describe such differences and highlights the chemical peculiarities of these types of N-heterocyclic carbene complexes. It introduces, in a qualitative manner, the synthetic routes that have been established for the preparation of such complexes, covering the literature from the very beginning of activities in this area up to 2008. While specialized reviews on some aspects of the present topic have recently appeared, 7 a comprehensive overview of the subject has not been available thus far. Rather than just being descriptive, the present account is mainly directed toward the impact of these still unusual metal-carbene bonding modes on the electronic properties and on the new catalytic applications that have been realized by employing such new carbene complexes. As a consequence of our focus on complexes with less-stabilized heterocyclic ligands, systems comprising acyclic carbenes have not been included, and the interested reader is, instead, referred to the pioneering and

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Section: Scheme 49mentioning

confidence: 99%

Beyond ConventionalN-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization

et al. 2009

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“…Depending on the ring substitution pattern, both 2-and 4-pyridylidene complexes have been prepared by such a rearrangement. [30][31][32][33][34] In contrast, C-H activation of N-alkylated pyridinium precursors that could allow for C2-or C4-coordination, exclusively leads to metallation at the 4-position. [35][36][37][38][39] This observation has been attributed to the steric bulk of the N-alkyl group.…”

Section: Introductionmentioning

confidence: 99%

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

et al. 2010

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“…CO usually replaces an ancillary ligand when it reacts with PCP rhodium(i) complexes. [17,18] For example, [(DiPPX)RhPEt 3 ] (DiPPX = diisopropylphosphinoxylene) reacts with one equivalent of CO in benzene to give [(DiPPX)RhCO] (see Experimental Section for details). Reversible formation of NCN d 8 ML 5 (M = Pt, Ni) was previously reported.…”

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confidence: 99%

π‐Accepting‐Pincer Rhodium Complexes: An Unusual Coordination Mode of PCP‐Type Systems

Kossoy

Iron

Rybtchinski

et al. 2005

Chemistry A European J

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The novel pi-accepting, pincer-type ligand, dipyrrolylphoshinoxylene (DPyPX), is introduced. This ligand has the strongest pi-accepting phosphines used so far in the PCP family of ligands and this results in some unusual coordination chemistry. The rhodium(I) complex, [(DPyPX)Rh(CO)(PR3)] (4, R=Ph, Et, pyrrolyl) is prepared by treating the relevant [(DPyPX)Rh(PR3)] (3) complex with CO and is remarkably resistant to loss of either ligand. X-ray crystallographic analysis of complex 4 b (R=Et) reveals an unusual cisoid coordination of the PCP phosphine ligands. These observations are supported by density functional theory (DFT) calculations.

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Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand

Cited by 61 publications

References 38 publications

Beyond ConventionalN-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization

Beyond ConventionalN-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands with Reduced Heteroatom Stabilization

Pyridine-Derived N-Heterocyclic Carbenes: An Experimental and Theoretical Evaluation of the Bonding in and Reactivity of Selected Normal and Abnormal Complexes of Nickel(II) and Palladium(II)

π‐Accepting‐Pincer Rhodium Complexes: An Unusual Coordination Mode of PCP‐Type Systems

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