Ligand substitution kinetics in M(CO)4 (η2:2-1,5-cyclooctadiene) complexes (M=Cr, Mo, W) — substitution of 1,5-cyclooctadiene by bis(diphenylphosphino)alkanes

Kayran, Ceyhan; Kozanoglu, Ferda; Özkâr, Saim; Saldamlı, Saltuk; Tekkaya, Ayşin; Kreiter, Cornelius G.

doi:10.1016/s0020-1693(98)00293-x

Cited by 12 publications

(6 citation statements)

References 25 publications

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“…Thus, the three ν CO resonances in complexes 1 – 3 most likely result from coincidental degeneracy of two separate bands. A similar effect has been seen in the group 6 phosphine complexes of Özkar and co-workers …”

Section: Resultsmentioning

confidence: 97%

“…A similar effect has been seen in the group 6 phosphine complexes of O ̈zkar and co-workers. 15 The ν CO stretching frequencies of 1−6 are higher than those in the aryl phosphines of O ̈zkar, which suggests that the bridging EAr iPr 4 units are better π acceptors than aryl phosphines. The ν CO stretching frequencies of 1−6 can also be compared to those of ethylenediamine (en) complexes with the formula M(en)(CO) 4 (M = Cr, Mo, W) reported by Kraihanzel and Cotton.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr^iPr₄)₂ (E = Ge, Sn; Ar^iPr₄ = C₆H₃-2,6(C₆H₃-2,6-ⁱPr₂)₂) by Reaction with Group 6 Carbonyls

et al. 2016

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The reactions of heavier group 14 element alkyne analogues (EAr iPr4 )2 (E = Ge, Sn; Ar iPr4 = C6H3-2,6-(C6H3-2,6-i Pr2)2) with the group 6 transition metal carbonyls M(CO)6 (M = Cr, Mo, W)under UV irradiation resulted in the cleavage of the E-E bond and the formation of complexes {Ar iPr4 EM(CO)4}2 (1-6) that were characterized by single crystal X-ray diffraction as well as by IR and multinuclear NMR spectroscopies. Single crystal X-ray structural analyses of 1-6 showed that the complexes have a nearly planar rhomboid M2E2 core with three-coordinate group 14 atoms. The coordination geometry at the group 6 metals is distorted octahedral formed by four carbonyl groups as well as two bridging EAr iPr4 units. IR spectroscopic data suggest that the EAr iPr4 units are not very efficient -acceptors, but the investigation of E-M metal-metal interactions in 1-6 with computational methods revealed the importance of both σ-and -type contributions to bonding. The mechanism for the insertion of transition metal carbonyls into E-E bonds in (EAr iPr4 )2 was also probed computationally.2

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Section: Resultsmentioning

confidence: 97%

Section: ■ Results and Discussionmentioning

confidence: 99%

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr^iPr₄)₂ (E = Ge, Sn; Ar^iPr₄ = C₆H₃-2,6(C₆H₃-2,6-ⁱPr₂)₂) by Reaction with Group 6 Carbonyls

et al. 2016

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“…Elemental analyses were carried out at London Metropolitan University. Starting materials 6Mes,21a 6Dipp,21a H 3 Al⋅IPr,13c [M(CO) 4 (COD)] (M=Cr, Mo, W),21b, c H 2 Ga{(NDippCMe) 2 CH},14b and H 2 Al{(NDippCMe) 2 CH}14a were prepared by previously reported procedures. The syntheses of complexes 2 a / b and 5 a / b were reported by us previously 11b,c.…”

Section: Methodsmentioning

confidence: 99%

Coordination and Activation of AlH and GaH Bonds

Abdalla

Riddlestone

Turner

et al. 2014

Chemistry A European J

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The modes of interaction of donor-stabilized Group 13 hydrides (E=Al, Ga) were investigated towards 14- and 16-electron transition-metal fragments. More electron-rich N-heterocyclic carbene-stabilized alanes/gallanes of the type NHC⋅EH3 (E=Al or Ga) exclusively generate κ(2) complexes of the type [M(CO)4 (κ(2)-H3 E⋅NHC)] with [M(CO)4 (COD)] (M=Cr, Mo), including the first κ(2) σ-gallane complexes. β-Diketiminato ('nacnac')-stabilized systems, {HC(MeCNDipp)2 }EH2 , show more diverse reactivity towards Group 6 carbonyl reagents. For {HC(MeCNDipp)2 }AlH2, both κ(1) and κ(2) complexes were isolated, while [Cr(CO)4 (κ(2)-H2 Ga{(NDippCMe)2 CH})] is the only simple κ(2) adduct of the nacnac-stabilized gallane which can be trapped, albeit as a co-crystallite with the (dehydrogenated) gallylene system [Cr(CO)5 (Ga{(NDippCMe)2 CH})]. Reaction of [Co2 (CO)8] with {HC(MeCDippN)2 }AlH2 generates [(OC)3 Co(μ-H)2 Al{(NdippCme)2 CH}][Co(CO)4] (12), which while retaining direct AlH interactions, features a hitherto unprecedented degree of bond activation in a σ-alane complex.

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“…The thermal substitution of 1,5-cyclooctadiene (COD) by bis(diphenylphosphino)alkanes , (C6H5)2P(CH2)nP(C6H5)2 (n = 1, 2, 3) in M(CO)4(η 2:2 -COD) complexes (M = Cr, Mo, W), were studied by Kayran et al [67]. The reactions of Cr(CO)4(COD) and Mo(CO)4(NBD) with h5-Cp*Ir(2,5-dimethylthiophene) give modest amounts of the [h6-Cp*Ir(C,S-2,5-Me2T)]M(CO)3 products [68].…”

Section: M(co)4 Codmentioning

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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Ligand substitution kinetics in M(CO)4 (η2:2-1,5-cyclooctadiene) complexes (M=Cr, Mo, W) — substitution of 1,5-cyclooctadiene by bis(diphenylphosphino)alkanes

Cited by 12 publications

References 25 publications

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr^iPr₄)₂ (E = Ge, Sn; Ar^iPr₄ = C₆H₃-2,6(C₆H₃-2,6-ⁱPr₂)₂) by Reaction with Group 6 Carbonyls

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr^iPr₄)₂ (E = Ge, Sn; Ar^iPr₄ = C₆H₃-2,6(C₆H₃-2,6-ⁱPr₂)₂) by Reaction with Group 6 Carbonyls

Coordination and Activation of AlH and GaH Bonds

The chemistry of group-VIb metal carbonyls

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Ligand substitution kinetics in M(CO)4 (η2:2-1,5-cyclooctadiene) complexes (M=Cr, Mo, W) — substitution of 1,5-cyclooctadiene by bis(diphenylphosphino)alkanes

Cited by 12 publications

References 25 publications

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAriPr4)2 (E = Ge, Sn; AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) by Reaction with Group 6 Carbonyls

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAriPr4)2 (E = Ge, Sn; AriPr4 = C6H3-2,6(C6H3-2,6-iPr2)2) by Reaction with Group 6 Carbonyls

Coordination and Activation of AlH and GaH Bonds

The chemistry of group-VIb metal carbonyls

Contact Info

Product

Resources

About

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr^iPr₄)₂ (E = Ge, Sn; Ar^iPr₄ = C₆H₃-2,6(C₆H₃-2,6-ⁱPr₂)₂) by Reaction with Group 6 Carbonyls

Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr^iPr₄)₂ (E = Ge, Sn; Ar^iPr₄ = C₆H₃-2,6(C₆H₃-2,6-ⁱPr₂)₂) by Reaction with Group 6 Carbonyls