Reactions of nickel-group 6 complexes with a bulky terminal alkyne to afford alkyne–carbonyl coupled products: X-ray structure of the heterobimetallic nickelacyclobutenone complex [(η5-C5Me5)Mo(CO)2(η5-C5H4Me)] (Ni–Mo)

Brenner, Éric; Chetcuti, Michael J.; Dridi, Ibtissem; Welter, Richard

doi:10.1016/j.jorganchem.2007.07.020

Cited by 5 publications

(2 citation statements)

References 34 publications

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“…Although it seems that no complex with bridging aminocarbene-iminoacyl ligands has been previously reported, we can relate the coordination of the ligand in 6 to that of the alkenyl-acyl ligands (μ- C , C ′: C , C ″-CRCR′C(O) coordination) resulting from the well documented CO–alkyne coupling at different dimetal centers . This similarity applies even to the fact that the C11N2C3W1 ring is almost flat, comparable to the metallacyclobutenone rings formed in the mentioned alkyne derivatives.…”

Section: Resultsmentioning

confidence: 55%

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂] with Isocyanides

et al. 2013

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The title complex reacted with stoichiometric amounts of CNR rapidly at room temperature or below to give two types of formimidoyl derivatives: the symmetrically bridged complexes [W 2 Cp 2 (μ-C,N:C,N-HCNR)(μ-PCy 2 )(CO) 2 ] (R = t Bu (W−W = 2.8645(5) Å), 4-C 6 H 4 OMe), and the asymmetrically bridged [W 2 Cp 2 {μ-C:N-HCN(Xyl)}(μ-PCy 2 )(CO) 2 ] (Cp = η 5 -C 5 H 5 ; Xyl = 2,6-C 6 H 3 Me 2 ). The latter complex underwent slow isomerization at room temperature to give the corresponding aminocarbyne derivative [W 2 Cp 2 {μ-CNH(Xyl)}(μ-PCy 2 )(CO) 2 ], which in turn could be decarbonylated through irradiation with UV−vis light to yield the 30-electron aminocarbyne complex [W 2 Cp 2 {μ-CNH(Xyl)}(μ-PCy 2 )(μ-CO)] (W−W = 2.4928(4) Å). Density functional theory calculations revealed that the aminocarbyne complex was the most stable isomer for the three isocyanides under study, while subtle steric effects marked the relative stability of the formimidoyl isomers, which therefore are the kinetic products of these reactions. The reaction of the title complex with excess CN(4-C 6 H 4 OMe) at room temperature gave in good yield the complex [W 2 Cp 2 (μ-C,N:C,C′-HCN(4-C 6 H 4 OMe)C{N(4-C 6 H 4 OMe)})(μ-PCy 2 )(CO) 2 ] (W−W = 2.9370(2) Å), having a 5-electron donor aminocarbene-iminoacyl ligand derived from the N−C coupling of formimidoyl and isocyanide ligands, whereas the analogous reaction with CNXyl gave the aminocarbyne complex [W 2 Cp 2 {μ-CNH(Xyl)}(μ-PCy 2 ){CN(Xyl)}(CO)] (W−W = 2.677(2) Å) having a terminal bent isocyanide ligand.

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Section: Resultsmentioning

confidence: 55%

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂] with Isocyanides

et al. 2013

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“…The nickel-molybdenum complex [(η 5 -C5Me5)Ni=Mo(CO)3(η 5 -C5H4Me)] can be considered to contain a partially dative nickelmolybdenum double bond. This complex reacts with the bulky terminal alkyne HC≡CCPh2(OMe) (DPMP) to afford the alkynecarbonyl coupled metallacyclic product (Sche me 56) (R = CPh2(OMe), Ni-Mo) regioselectively and exclusively [210].…”

Section: Scheme 54mentioning

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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Cyclopentadienyl Nickel Complexes

Włodzimierz

2022

Comprehensive Organometallic Chemistry IV

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Reactions of nickel-group 6 complexes with a bulky terminal alkyne to afford alkyne–carbonyl coupled products: X-ray structure of the heterobimetallic nickelacyclobutenone complex [(η5-C5Me5)Mo(CO)2(η5-C5H4Me)] (Ni–Mo)

Cited by 5 publications

References 34 publications

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂] with Isocyanides

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂] with Isocyanides

The chemistry of group-VIb metal carbonyls

Cyclopentadienyl Nickel Complexes

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Reactions of nickel-group 6 complexes with a bulky terminal alkyne to afford alkyne–carbonyl coupled products: X-ray structure of the heterobimetallic nickelacyclobutenone complex [(η5-C5Me5)Mo(CO)2(η5-C5H4Me)] (Ni–Mo)

Cited by 5 publications

References 34 publications

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W2(η5-C5H5)2(H)(μ-PCy2)(CO)2] with Isocyanides

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W2(η5-C5H5)2(H)(μ-PCy2)(CO)2] with Isocyanides

The chemistry of group-VIb metal carbonyls

Cyclopentadienyl Nickel Complexes

Contact Info

Product

Resources

About

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂] with Isocyanides

Insertion, Rearrangement, and Coupling Processes in the Reactions of the Unsaturated Hydride Complex [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂] with Isocyanides