Nucleophilic displacement of ethylene from π-C5H5Rh(C2H4)2

Cramer, Richard D.; Seiwell, Linda P.

doi:10.1016/s0022-328x(00)92096-5

Cited by 51 publications

(21 citation statements)

References 11 publications

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“…More readily interpreted, because after the nitrosyl experience we were prepared to localize a pair of electrons on the cyclopentadienyl ring in order to permit nucleophilic attack of a low energy metal orbital. Some years later it was suggested [136] that the pair of electrons localized on the cyclopentadienyl ring could be formulated as an ƞ 3 allyl-ene system. There isnow X-ray evidence [137] for such a cyclic ligand in the compound (ƞ 5 -C5H5)(ƞ 3 -C5H5)W(CO)2.…”

Section: Scheme 24mentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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KEYWORDSThe special interest attached to the chemistry of metal carbonyls arises from several causes. While quite distinct from the metal carbonyls in the organometallic compounds, they differ in physical properties (e.g., their volatility) from all other compounds of the transition metals. Chemically, they constitute a group of compounds in which the formal valency of the metal atoms is zero, and in this respect (apart, perhaps, from the ammoniates of the alkali metals) they are comparable only with the recently discovered compounds. As a class, the carbonyls are reactive compounds, and a number of new types of inorganic compounds have been discovered. In the concepts for new products, performance, product safety, and product economy criteria are equally important. They are taken into account already when the raw material base for a new industrial product development is defined. Since the discovery of nickel carbonyl by Mond and Langer in 1888, the carbonyls of the iron group and of chromium, molybdenum and tungsten have found important technical applications, e.g., in the Mond nickel process, and for the preparation of the metals in a state of subdivision and of purity suitable for powder metallurgy, for catalysts, etc. The reaction mechanism of the processes developed for producing the carbonyls technically has only recently received its interpretations. Within the space of review it is necessary to limit discussion to a few topics. Particular stress has accordingly laid upon (a) the chemical bonding in metal carbonyls, (b) importance of IR and NMR spectroscopy in characterization of metal carbonyls, (c) substitution reactions of G-VIb metal carbonyls, (d) kinetics and mechanism of substitution reactions in metal carbonyls, (e) substituted complexes of G-VIb metal carbonyl, (f) chelate complexes of G-VIb metal carbonyls, (g) uses of G-VIb metal carbonyl complexes and (h) studies done on G-VIb metal carbonyls.

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Section: Scheme 24mentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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“…Nevertheless, the possibility of the occurrence of η 3 intermediates has been postulated frequently as a mechanistic rationale for a number of organometallic rearrangement reactions, simply to adhere to the 18e rule. Among such reactions are α- and β-hydrogen abstractions, , photochemically induced C−H, Si−H, and C−C bond cleavages, cyclopentadienyl ligand transfers, and ligand substitution. 3d, Surprisingly, for inter- or intramolecular nucleophilic attack at C 5 H 5 ligands, transient η 3 or η 1 coordination has hitherto not been considered, despite the fact that η 5 -C 5 H 5 is known to be rather inert toward nucleophilic attack …”

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confidence: 99%

Activation of η⁵-Cyclopentadienyl Ligands toward Nucleophilic Attack through η⁵ → η³ Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy

et al. 1998

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“…17 The intermediate 10 dissociates into [(C 2 Me 2 ) 3 Rh] + (11) and free benzene without traceable barrier. Apparently, the unsaturated complex 11 then coordinates with additional alkyne molecules, eventually giving fully substituted cyclobutadiene arene complex [(C 4 Me 4 )Rh-(C 6 Me 6 )] + (12), an analogue of the experimentally observed [(C 4 Et 4 )Rh(C 6 Et 6 )] + (1e).…”

Section: ■ Results and Discussionmentioning

confidence: 91%

“…The substitution probably proceeds via an associative mechanism; dissociative substitution is unlikely because it would require heating above 100 °C, as in the case of the related complex CpRh(C 2 H 4 ) 2 . 12 In order to prepare rhodium complexes with functionally substituted arenes, we studied the ligand exchange in the cation 1a (Scheme 2). It was found that heating of 1a with 4-methylaniline or 2-mesitylacetonitrile at 60 °C in acetone cleanly gives the corresponding complexes 1f,g.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Cyclobutadiene Arene Complexes of Rhodium and Iridium

et al. 2016

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Reactions of [(C2H4)2RhCl]2 or [(coe)2RhCl]2 (coe = cyclooctene) with AgPF6 and arenes, followed by addition of 3-hexyne, give the cyclobutadiene complexes [(C4Et4)Rh(arene)]+ in 40–65% yield (arene = tert-butylbenzene, p-xylene, mesitylene, 4-mesitylbutanoic acid). In the absence of arenes, the hexaethylbenzene complex [(C4Et4)Rh(C6Et6)]+ is formed in 70% yield as a result of cyclotrimerization of 3-hexyne in the coordination sphere of rhodium. Similar reaction of [(coe)2IrCl]2 with AgPF6 and 3-hexyne leads to [(C4Et4)Ir(C6Et6)]+, which is apparently the first reported cyclobutadiene iridium complex. DFT calculations suggest that formation of the model cyclobutadiene complex [(C4Me4)Rh(C6H6)]+ from bis(alkyne) intermediate [(C2Me2)2Rh(C6H6)]+ can proceed via a metallacycle transition state with a low energy barrier of 14.5 kcal mol–1.

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Nucleophilic displacement of ethylene from π-C5H5Rh(C2H4)2

Cited by 51 publications

References 11 publications

The chemistry of group-VIb metal carbonyls

The chemistry of group-VIb metal carbonyls

Activation of η⁵-Cyclopentadienyl Ligands toward Nucleophilic Attack through η⁵ → η³ Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy

Cyclobutadiene Arene Complexes of Rhodium and Iridium

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Nucleophilic displacement of ethylene from π-C5H5Rh(C2H4)2

Cited by 51 publications

References 11 publications

The chemistry of group-VIb metal carbonyls

The chemistry of group-VIb metal carbonyls

Activation of η5-Cyclopentadienyl Ligands toward Nucleophilic Attack through η5 → η3 Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy

Cyclobutadiene Arene Complexes of Rhodium and Iridium

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Activation of η⁵-Cyclopentadienyl Ligands toward Nucleophilic Attack through η⁵ → η³ Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy