1Pyridine and phosphine functionalised N-heterocyclic carbene complexes of rhodium and iridium

Stylianides, N. A.; Danopoulos, Andreas A.; Tsoureas, Nikolaos

doi:10.1016/j.jorganchem.2005.07.094

Cited by 100 publications

(54 citation statements)

References 36 publications

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“…[290] The specific type of donor in the donor-functionalized imodazolium salts appears to be of some importance for the course of the metalation. Peris et al [259] and Danopoulos et al [291] prepared iridium NHC complexes using pyridylfunctionalized imidazolium salts. The complexes contain exclusively C 2 -metalated NHC ligands.…”

Section: Abnormal Carbenesmentioning

confidence: 99%

“…However, the use of a very similar phosphine-functionalized imidazolium salt afforded the iridium complex with the C 5 -metalated NHC ligand. [291] Not only donor-functionalized but also monodentate imidazolium salts have been reported to form complexes with abnormal bound NHC ligands. The Ir III complex 172 is formed in good yield by selective metalation of the sterically least-hindered ring carbon atom, C 5 (Scheme 91).…”

Section: Abnormal Carbenesmentioning

confidence: 99%

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Heterocyclic Carbenes: Synthesis and Coordination Chemistry

2008

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The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of beta-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

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Section: Abnormal Carbenesmentioning

confidence: 99%

Section: Abnormal Carbenesmentioning

confidence: 99%

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

2008

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“…46 Metal-hydride formation could perhaps play an important role in the unexpected carbene rearrangement when using iridium precursors. However, further studies are required to evaluate other potential reaction pathways, such as proton migration from C4 to C2 during metallation.…”

Section: Coordination To Free Carbenesmentioning

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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“…The bond lengths are in the range previously reported for similar complexes. [10] The availability of the dangling indene in 3b and 3c pointed to the possibility of a rational construction of bimetallic complexes by subsequent deprotonation of the indene followed by reaction with electrophilic metal precursors. Although deprotonation of 3b and 3c (for example by alkyllithium compounds) was evident, in most cases intractable mixtures were obtained after the addition of the metal electrophile.…”

Section: Me4mentioning

confidence: 99%

Indenyl‐ and Fluorenyl‐Functionalized N‐Heterocyclic Carbene Complexes of Rhodium and Iridium – Synthetic, Structural and Catalytic Studies

et al. 2009

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Rhodium and iridium complexes with N‐heterocyclic carbenes (NHC) functionalized with neutral or anionic indenyl and fluorenyl groups are reported. In the complexes the ligands adopt monodentate, bidentate or bridging bonding modes with the NHC group σ‐bonded and the fluorenyl or indenyl functionalities either dangling or coordinated to the metal with various hapticities (η1, η3 and η5). Metallation of the C–H bond of the alkylene linker in the ligand has also been observed. Catalytic studies on the bidentate RhI complex 6 show that it is weakly active for the hydroformylation of 1‐octene with poor linear selectivity, but it shows slightly lower activity than the standard Monsanto system for the carbonylation of methanol.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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1Pyridine and phosphine functionalised N-heterocyclic carbene complexes of rhodium and iridium

Cited by 100 publications

References 36 publications

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

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

Indenyl‐ and Fluorenyl‐Functionalized N‐Heterocyclic Carbene Complexes of Rhodium and Iridium – Synthetic, Structural and Catalytic Studies

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