Di‐μ‐Chloro‐Bis(η
            <sup>4</sup>
            ‐1,5‐Cyclooctadiene)‐Dirhodium(I)

Giordano, G.; Crabtree, R. H.; Heintz, R.; Forster, Denis; Morris, Donald E.

doi:10.1002/9780470132593.ch22

Cited by 378 publications

(93 citation statements)

References 3 publications

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“…[14] All other reagents are commercially available and were used as received. Solvents were taken from an Innovative Technology Pure Solvent Dispenser prior to use.…”

Section: Methodsmentioning

confidence: 99%

Four Soft Donors and a Hard Centre: Rhodium Complexes of a Novel Tetrakis(NHC)‐Encapsulated Crown Ether Ligand

et al. 2011

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2,3,13,14‐Tetrakis(bromomethyl)dibenzo‐18‐crown‐6 (1) has been demonstrated to be a versatile synthetic intermediate for constructing multinucleating ligands with a hard‐donor, crown ether centre. By using this intermediate, novel salts of tetrakis(imidazoliomethyl)dibenzo‐18‐crown‐6, [H4L1]X4 (2: X– = Br–; 4: X– = PF6–), and tetrakis(benzimidazoliomethyl)dibenzo‐18‐crown‐6, [H4L2]X4 (3: X– = Br–; 5: X– = PF6–), were prepared. These salts are precursors to novel tetrakis(N‐heterocyclic carbene) complexes spanned by a crown ether bridge capable of binding various hard metal ions. Thetetrakis(imidazoliomethyl) salt 4 was used to prepare the bimetallic rhodium complexes [{(cod)Rh}2(μ‐L1)][PF6]2 (6) and [{(CO)2Rh}2(μ‐L1)][PF6]2 (7). These complexes selectively bind alkali metal ions.

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“…[14] All other reagents are commercially available and were used as received. Solvents were taken from an Innovative Technology Pure Solvent Dispenser prior to use.…”

Section: Methodsmentioning

confidence: 99%

Four Soft Donors and a Hard Centre: Rhodium Complexes of a Novel Tetrakis(NHC)‐Encapsulated Crown Ether Ligand

et al. 2011

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“…(d, 3 J H,H = 8.9 Hz, 1H, Ar), 7.03 (m, 2H, Ar), 6.75 (dd, 3 J H,H = 7.6 Hz, 2H, Ar), 5.82 (br s, 1H, Ar), 3.59 (br s, 8H, -CH 2 of bound THF), 1.71 (br s, 8H, -CH 2 of bound THF), -19.84 (t, J Rh,H = 24.7 Hz, 2H, Rh-H). 13 C NMR (CD 2 Cl 2 ): 166.73 (d, 1 J Rh,C = 35.7 Hz, Rh-C ipso ), 155.41,147.39,146.99,146.63,141.88,141.10,140.90,138.80,136.90,136.73,133.94,129.97,129.76,128.64,127.92,127.15,127.05,126.55,124.06,123.36,122.62,121.94,121.72,121.25 (s,Ar), 68.79 (br s, -CH 2 of bound THF), 25.81 (s, -CH 2 of bound THF). 19 (3), from 20 degrees of data, T = 120(2) K, V = 6389(2) Å 3 , Z = 4, Fw = 1325.68 g/mol, D calc = 1.378 Mg m À3 , l = 0.822 mm À1 .…”

Section: Reaction Of [Rh(coe) 2 (Thf) 2 ][Bf 4 ] With Bhq-h (1) Formmentioning

confidence: 97%

“…[Rh (C 2 H 4 )Cl] 2 [11], [Rh(COE)Cl] 2 [12], [Rh(COD)Cl] 2 [13] and [Rh(COE) 2 (acetone) 2 ][PF 6 ] [14] were prepared according to literature procedures. The precursors [Rh(olefin) n (THF) 2 ][BF 4 ] (olefin = C 2 H 4 (n = 2), COE (n = 2) or COD (n = 1)) were prepared in situ by chloride abstraction from the corresponding l-chloro-bridged precursors according to a published procedure [15].…”

Section: General Proceduresmentioning

confidence: 99%

“…The precursors [Rh(olefin) n (THF) 2 ][BF 4 ] (olefin = C 2 H 4 (n = 2), COE (n = 2) or COD (n = 1)) were prepared in situ by chloride abstraction from the corresponding l-chloro-bridged precursors according to a published procedure [15]. 1 H, 13 C, 31 P and 0020-1693/$ -see front matter Ó 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2010.…”

Section: General Proceduresmentioning

confidence: 99%

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Aliphatic and aromatic C–H activation of benzo[h]quinolines by Rh(I). Unique precursor dependent formation of mono-, di- and trinuclear complexes

Salem

Leitus

Shimon

et al. 2011

Inorganica Chimica Acta

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“…DMSO was purchased as the dry solvent. [Rh(cod)Cl] 2 26 and imidazole aniline 27 were prepared according to literature procedures. Other reagents were obtained commercially and used as received.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Charge-Delocalized κ²C,N-NHC-Amine Complexes of Rhodium, Iridium, and Ruthenium

et al. 2014

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The development of a novel set of complexes bearing an NHC-amine ligand (C NHC -NH 2 ) is described. M(cod) complexes (M = Ir, Rh) and a Ru complex have been synthesized in which three different coordination modes of the ligand were established: monodentate, neutral bidentate, and anionic bidentate. The anionic bidentate coordination mode of the anionic C NHC -NH − ligand arises from deprotonation of the amine moiety of the neutral C NHC -NH 2 ligand. Ligand deprotonation proved to be reversible for the Rh and Ir complexes, as was shown by subsequent treatment of the complexes with base and acid. The structural parameters of these differently coordinated ligands were examined, and it was shown that the conjugation of the aniline ring plays a major role in determining the ligand properties. ■ INTRODUCTIONThe use of carbenes as ligands is well developed in the field of transition-metal complex chemistry.1 In particular, the Nheterocyclic carbene (NHC) class of imidazol-2-ylidines, first reported in the 1960s, 2 have received their fair share of attention. Many successful examples of the application of NHCs in transition-metal-catalyzed transformations such as hydrogenations and metathesis reactions 3−5 have been reported. We recently reported on the synthesis of a conjugated NHC-amine ligand species where an NHC is conjugated with an aniline (C NHC -NH 2 ). 6 In this species, the primary amine is tethered to the NHC via an aromatic ring. The amine moiety of our C NHC -NH 2 ligand A (see Figure 1) can coordinate in a neutral or in an anionic fashion (when deprotonated). Monoanionic (bidentate) ligands have found widespread application in homogeneous catalysis. The most recognized are (pentamethyl)cyclopentadienyl (Cp, Cp*), acetylacetonate (acac), and diketimine (nacnac, where the two oxygen atoms of acac have been replaced by nitrogen-based moieties of the form NR). 7,8 Well-known examples of bifunctional ligands are ligands containing hydroxyl or oxime 9 groups and pincer-type ligands containing an anionic donor arm. 10,11 Previous work by Morris, involving a benzylic amine tethered to an NHC, has shown the ability of this ligand scaffold to display cooperativity, but this depended greatly on other factors such as the ancillary ligand (p-cym vs Cp*) and solvent assistance.12 Morris also explored the potential of iridium(I)-cod complexes containing neutral bidentate NHC-benzylic amine ligands, coordinated as seven-membered chelate rings to the metal center. Anilinebased C NHC -NH 2 ligands, forming neutral complexes containing conjugated anionic C NHC -NH − ligands bound to Rh, Ir, or

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Di‐μ‐Chloro‐Bis(η ⁴ ‐1,5‐Cyclooctadiene)‐Dirhodium(I)

Cited by 378 publications

References 3 publications

Four Soft Donors and a Hard Centre: Rhodium Complexes of a Novel Tetrakis(NHC)‐Encapsulated Crown Ether Ligand

Four Soft Donors and a Hard Centre: Rhodium Complexes of a Novel Tetrakis(NHC)‐Encapsulated Crown Ether Ligand

Aliphatic and aromatic C–H activation of benzo[h]quinolines by Rh(I). Unique precursor dependent formation of mono-, di- and trinuclear complexes

Charge-Delocalized κ²C,N-NHC-Amine Complexes of Rhodium, Iridium, and Ruthenium

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Di‐μ‐Chloro‐Bis(η 4 ‐1,5‐Cyclooctadiene)‐Dirhodium(I)

Cited by 378 publications

References 3 publications

Four Soft Donors and a Hard Centre: Rhodium Complexes of a Novel Tetrakis(NHC)‐Encapsulated Crown Ether Ligand

Four Soft Donors and a Hard Centre: Rhodium Complexes of a Novel Tetrakis(NHC)‐Encapsulated Crown Ether Ligand

Aliphatic and aromatic C–H activation of benzo[h]quinolines by Rh(I). Unique precursor dependent formation of mono-, di- and trinuclear complexes

Charge-Delocalized κ2C,N-NHC-Amine Complexes of Rhodium, Iridium, and Ruthenium

Contact Info

Product

Resources

About

Di‐μ‐Chloro‐Bis(η ⁴ ‐1,5‐Cyclooctadiene)‐Dirhodium(I)

Charge-Delocalized κ²C,N-NHC-Amine Complexes of Rhodium, Iridium, and Ruthenium