Photochemisch induzierte oxidative addition von aldehyden an dekacarbonyldirhenium(0)

Kreiter, Cornelius G.; Franzreb, Karl-Heinz; Sheldrick, William S.

doi:10.1016/0022-328x(84)80336-8

Cited by 10 publications

(9 citation statements)

References 14 publications

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“…30 min). The formation of [Re 2 (μ-H)(μ-CHC(H)Ph)(CO) 8 ] , from the reaction with styrene was slightly slower, reaching completion in about 20 min at 298 K. In the case of acetaldehyde, the reaction was still highly selective, but much slower, requiring about 2.5 h for the complete transformation of 3 into [Re 2 (μ-H)(μ-η 2 -C(Me)O)(CO) 8 ] …”

Section: Resultsmentioning

confidence: 99%

“…A sample of 3 ( 7.2 mg, 9.7 μmol) was dissolved in THF- d 8 , at 273 K, in a NMR tube and treated with 2.5 μL (44 μmol) of acetaldehyde. The progress of the reaction was followed by 1 H NMR spectroscopy, at room temperature, showing the progressive growth of the resonances of [Re 2 (μ-H)(μ-C(Me)O)(CO) 8 ] at δ −14.0 (1) and 2.57 (3) (lit . data: −14.01, 2.61).…”

Section: Methodsmentioning

confidence: 99%

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1,2-eq,eq-[Re₂(CO)₈(THF)₂]: A Reactive Re₂(CO)₈Fragment That Easily Activates H−H and C−H Bonds

Carlucci¹,

Proserpio²,

D’Alfonso³

1999

Organometallics

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The reaction of [Re2(μ-H)2(CO)8] (1) with diazomethane at 193 K in THF-d 8 gives the unstable [Re2(μ-H)(μ-CH3)(CO)8] derivative (2) containing a methyl group arising from the insertion of CH2 into a Re−H−Re bond. Isotopic perturbation of the equilibria by partial deuteration demonstrated that the methyl bridges the Re−Re bond in an unsymmetrical way, with a fast exchange between one agostic and two terminal C−H bonds. At temperatures higher than 253 K, 2 decomposes, in THF solution, with CH4 elimination to give the novel red complex 1,2-eq,eq-[Re2(CO)8(THF)2] (3), which was characterized by NMR spectroscopy and X-ray analysis. In the solid form a staggered conformer of C 2 symmetry was found. 13C NMR analysis revealed the presence, in wet THF, of the aquo complexes [Re2(CO)8(THF)(H2O)] (4) and [Re2(CO)8(H2O)2] (5), whose formation is favored at low temperature (ΔH° for the formation of 5 from 4: −14.4(2) kJ mol-1). In solution, due to the lability of the THF ligands, 3 behaves as a “lightly stabilized” Re2(CO)8 fragment, capable of activating different E−H bonds. Reaction with HCl in THF leads to [Re2(μ-H)(μ-Cl)(CO)8], while with H2 the unsaturated starting material [Re2(μ-H)2(CO)8] is obtained. In THF solution, at room temperature, reactions with phenylacetylene, styrene, and acetaldehyde give the derivatives of C−H activation [Re2(μ-H)(μ-C⋮CPh)(CO)8], [Re2(μ-H)(μ-CHC(H)Ph)(CO)8], and [Re2(μ-H)(μ-η2-C(Me)O)(CO)8]. Moreover, the activation of an sp3 C−H bond in ethyl acetate occurs slowly when 3 is dissolved in the reactant itself, the resultant product being [Re2(μ-H)(μ-η2-CH2C(O)OEt)(CO)8].

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

1,2-eq,eq-[Re₂(CO)₈(THF)₂]: A Reactive Re₂(CO)₈Fragment That Easily Activates H−H and C−H Bonds

Carlucci¹,

Proserpio²,

D’Alfonso³

1999

Organometallics

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“…Possible route for the formation of complexes 1 and 2 may be envisaged. It is proposed that [Re 2 (CO) 8 (MeCN) 2 ] dissociates into coordinatively unsaturated species [Re 2 (CO) 8 (MeCN)]. Thiazole coordinates via a r-N bond to form g 1 -[Re 2 (CO) 8 (MeCN)(g 1 -thiazole)] which then further dissociates and a second thiazole moiety becomes coordinated to form [Re 2 (CO) 7 (MeCN)(g 1 -thiazole) 2 ].…”

Section: Discussionmentioning

confidence: 99%

“…Binuclear complexes bridged by multidentate ligands have been the subjects of considerable amount of work in the last two decades [2]. Rhenium complexes of the general formula [Re 2 (l-Y)(CO) 8 (l-H)] (Y = PR 2 [3], Cl, I [4], g 2 -pyridyl [5], g 2 -C"CR [6], g 2 -C@CRR 0 [7], C(R)O [8], SR [9]) are well known in organometallic chemistry. Currently, there is considerable interest in the reactivity of N-and S-containing aromatic heterocyclic molecules with transition metal carbonyl compounds because the presence of more than one type of donor atoms in such ligands can introduce novel reactivity and frequently stabilizes the metal cluster frame work by serving as bridging or chelating ligands [10].…”

Section: Introductionmentioning

confidence: 99%

Reactivity of [Re2(CO)8(MeCN)2] with thiazoles: Hydrido bridged dirhenium compounds bearing thiazoles in different coordination modes

Kabir

Ahmed

Das

et al. 2007

Journal of Organometallic Chemistry

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Reactions of the labile compound [Re 2 (CO) 8 (MeCN) 2 ] with thiazole and 4-methylthiazole in refluxing benzene afforded the new compounds [Re 2 (CO) 7 {l-2,3-g 2 -C 3 H(R)NS}{g 1 -NC 3 H 2 (4-R)S}(l-H)] (1, R = H; 2, R = CH 3 ), [Re 2 (CO) 6 {l-2,3-g 2 -C 3 H(R)NS}{g 1 -NC 3 H 2 (4-R)S} 2 (l-H)] (3, R = H; 4, R = CH 3 ) and fac-[Re(CO) 3 (Cl){g 1 -NC 3 H 2 (4-R)S} 2 ] (5, R = H; 6, R = CH 3 ). Compounds 1 and 2 contain two rhenium atoms, one bridging thiazolide ligand, coordinated through the C(2) and N atoms and a g 1 -thiazole ligand coordinated through the nitrogen atom to the same Re as the thiazolide nitrogen. Compounds 3 and 4 contain a Re 2 (CO) 6 group with one bridging thiazolide ligand coordinated through the C(2) and N atoms and two N-coordinated g 1 -thiazole ligands, each coordinated to one Re atom. A hydride ligand, formed by oxidative-addition of C(2)-H bond of the ligand, bridges Re-Re bond opposite the thiazolide ligand in compounds 1-4. Compound 5 contains a single rhenium atom with three carbonyl ligands, two N-coordinated g 1 -thiazole ligands and a terminal Cl ligand. Treatment of both 1 and 2 with 5 equiv. of thiazole and 4-methylthiazole in the presence of Me 3 NO in refluxing benzene afforded 3 and 4, respectively. Further activation of the coordinated g 1 -thiazole ligands in 1-4 is, however, unsuccessful and results only nonspecific decomposition. The single-crystal XRD structures of 1-5 are reported.

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“…Rhenium complexes of the general formula [Re 2 (µ-H)-(µ-Y)(CO) 8 ] (Y = PR 2 , 1 Cl, I, 2 η 2 -pyridyl, 3 η 2 -C᎐ ᎐ ᎐ CR, 4 η 2 -CH᎐ ᎐ CRRЈ, 5 C(R)O 6 ) are well known in organometallic chemistry. Especially the reactivity of the hydrido phosphido bridged complexes has been studied intensively over the last years with respect to cluster synthesis 7 and cluster catalysis.…”

Section: Introductionmentioning

confidence: 99%

The reaction of [Re2(CO)8(MeCN)2] with thiols. Formation of hydrido sulfido bridged dirhenium cluster complexes [Re2(μ-H)(μ-SR)(CO)8] (R = H, n-Bu, Cy, Ph, C6H4F-p, C6F5 or 2-naphthyl)

Egold¹,

Schwarze²,

Flörke³

1999

J. Chem. Soc., Dalton Trans.

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The complex [Re 2 (CO) 8 (MeCN) 2 ] 1 reacted with thiols or H 2 S, respectively, by SH oxidative addition in toluene at 80 ЊC to give hydrido sulfido bridged dirhenium complexes of the general formula [Re 2 (µ-H)(µ-SR)(CO) 8 ] (R = H 2a, n-Bu 2b, Cy 2c, Ph 2d, C 6 H 4 F-p 2e, C 6 F 5 2f or 2-naphthyl 2g) in 60 to 80% yield. Complexes 2c and 2g have been characterised by crystal structure analysis. Complex 2a undergoes reaction with another equivalent of 1 to form the novel spirocyclic complex [{Re 2 (µ-H)(CO) 8 } 2 (µ 4 S)] 3. In order to demonstrate the acidity of the µ-H ligand 2g was deprotonated by the base 1,8-diazabicyclo[5.4.0]undec-7-ene to give the anion [Re 2 (µ-S(2-naph))(CO) 8 ] Ϫ 4 Ϫ (naph = naphthyl) which can be isolated as its PPh 4 ϩ salt. This reacts with one equivalent of [MCl(PPh 3 )] (M = Au, Ag or Cu) to give the novel heteronuclear cluster complexes [Re 2 (MPPh 3 )(µ-S(2-naph))(CO) 8 ] (M = Au 5a, Ag 5b or Cu 5c) and PPh 4 Cl. The molecular structures of 5a and 5b have been established by single crystal X-ray analysis.

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Photochemisch induzierte oxidative addition von aldehyden an dekacarbonyldirhenium(0)

Cited by 10 publications

References 14 publications

1,2-eq,eq-[Re₂(CO)₈(THF)₂]: A Reactive Re₂(CO)₈Fragment That Easily Activates H−H and C−H Bonds

1,2-eq,eq-[Re₂(CO)₈(THF)₂]: A Reactive Re₂(CO)₈Fragment That Easily Activates H−H and C−H Bonds

Reactivity of [Re2(CO)8(MeCN)2] with thiazoles: Hydrido bridged dirhenium compounds bearing thiazoles in different coordination modes

The reaction of [Re2(CO)8(MeCN)2] with thiols. Formation of hydrido sulfido bridged dirhenium cluster complexes [Re2(μ-H)(μ-SR)(CO)8] (R = H, n-Bu, Cy, Ph, C6H4F-p, C6F5 or 2-naphthyl)

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Photochemisch induzierte oxidative addition von aldehyden an dekacarbonyldirhenium(0)

Cited by 10 publications

References 14 publications

1,2-eq,eq-[Re2(CO)8(THF)2]: A Reactive Re2(CO)8Fragment That Easily Activates H−H and C−H Bonds

1,2-eq,eq-[Re2(CO)8(THF)2]: A Reactive Re2(CO)8Fragment That Easily Activates H−H and C−H Bonds

Reactivity of [Re2(CO)8(MeCN)2] with thiazoles: Hydrido bridged dirhenium compounds bearing thiazoles in different coordination modes

The reaction of [Re2(CO)8(MeCN)2] with thiols. Formation of hydrido sulfido bridged dirhenium cluster complexes [Re2(μ-H)(μ-SR)(CO)8] (R = H, n-Bu, Cy, Ph, C6H4F-p, C6F5 or 2-naphthyl)

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1,2-eq,eq-[Re₂(CO)₈(THF)₂]: A Reactive Re₂(CO)₈Fragment That Easily Activates H−H and C−H Bonds

1,2-eq,eq-[Re₂(CO)₈(THF)₂]: A Reactive Re₂(CO)₈Fragment That Easily Activates H−H and C−H Bonds