Carbon-carbon bond formation between two .alpha.-diimines with the simultaneous formation of a metal-metal bond. X-ray structure of hexacarbonylbis[.mu.-(1-(isopropylamino)-2-(isopropylimino)ethano-N,N')]-dimolybdenum

Staal, L.H.; Oskam, A.; Vrieze, K.; Roosendaal, E.; Schenk, H.

doi:10.1021/ic50196a050

Cited by 31 publications

(15 citation statements)

References 8 publications

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“…1) strongly reflect its quinoid character: thus the C(6)-C(7) and C(2)-C(3) distances are shortened while the other bond lengths are lengthened. The N(l)-C (2) and N(2)-C(5) distances are typical of a C-N double bond [16,20]. The N(2)-C(lO) distance of 1.42 A is not unusual for a N-Ph single bond, and may be compared with C-N distances reported for various anilines [ 18,191.…”

Section: Structure Of Mtqd In the Solid Statementioning

confidence: 98%

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X-ray structure and dynamic behaviour in solution of N-methylthio-N'-2,6-dimethylphenyl).2,6-dimethyl-1,4-quinonediimine formed by the alcoholysis of [Me2 Al{2,6-Me2C6H3NS(Me)NC6H3Me2-2,6}]2

Klerks

Koten

Vrieze

et al. 1981

Journal of Organometallic Chemistry

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Reaction of [Me2A1{RNS(Me)NRj], (R = 2,6-Me&H,) with t-BuOH affords N-methylthio-N'-(2,6-dimethylphenyl)-2,6-dimethyl-l,4-quinonediirnine in 67% yield. The X-ray structure of this compound shows that two confo~ational isomers are present in the solid. Temperature dependent 13C and 'H NMR measurements show that in solution these conformers exchange at a rate which is fast on the NMR time scale at +6O"C and slow at -60°C. From the coalescence point of two of the 13C resonances, the free energy of activation is estimated to be 13.7 + 1.0 kcallmol at 10°C. Possible processes for the exchange are discussed, and also a reaction scheme for the formation of the title compound is discussed.

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Section: Structure Of Mtqd In the Solid Statementioning

confidence: 98%

“…Study of models shows that the formation of such an intermediate would be favoured by the fact that it has a conformation with minimal sterical hindrance. The subsequent steps in the reaction scheme involve N-S bond cleavage, migration of the [2, unit, and abstraction of two hydrogen atoms.…”

Section: Dynamical Behaviour Of Mtqd In Solutionmentioning

confidence: 99%

X-ray structure and dynamic behaviour in solution of N-methylthio-N'-2,6-dimethylphenyl).2,6-dimethyl-1,4-quinonediimine formed by the alcoholysis of [Me2 Al{2,6-Me2C6H3NS(Me)NC6H3Me2-2,6}]2

Klerks

Koten

Vrieze

et al. 1981

Journal of Organometallic Chemistry

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“…The first observed complex containing the IAE ligand is Mo,(CO),&AE), which was prepared by the following two routes [30].…”

Section: Coupling Of Two R-dab Ligands To Form the Iae Ligand (Iae = mentioning

confidence: 99%

“…The bond distance of the single MO-MO bond is 2.813(3) A. The C-C bond lengths of the C-C bond linking the two R-DAB units is 1.61(2) A [30]. This C-C bond may be cleaved again by heating or irradiating the complex in solution.…”

Section: Coupling Of Two R-dab Ligands To Form the Iae Ligand (Iae = mentioning

confidence: 99%

“…It is remarkable that Cr,(CO)&U) could be prepared in only very small yields, while the tungsten analogue could not be formed at all by the above reactions [30]. This is probably due to the inherent lability of the C-C bonds with respect to bond breaking, as will be discussed later for Ru [20] and Zn [3 11.…”

Section: Coupling Of Two R-dab Ligands To Form the Iae Ligand (Iae = mentioning

confidence: 99%

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Metal heterodiene complexes

Vrieze

Koten

1985

Inorganica Chimica Acta

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In this article a survey is given of novel results in the field of the chemistry of a-diimine complexes of some metal atoms of the main group, transition metal and post transition metal area. It is shown that a-diimines of the type RN=C(R')(R")C=NR (= R-DAB) and 2C&NC(R')=NR (= R-Pyca) are very versatile with regards to both their coordination chemistry and chemical reactivity when coordinated to a metal or metal cluster. The type of reaction occurring depends critically on the type of metal(s), the other ligands present on the metal(s), the type of coordination of the a-diimines, and particularly on the steric and electronic properties of R,R' and R" situated on the R-DAB and R-Pyca ligands.

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Preparation and Properties of Carbonyliron Complexes of 1-Aza-4-oxa-1,3-butadiene (α-Imino Ketone) – X-ray Crystal Structures of Fe(CO)3[MeNC(Ph)C(Ph)=O] and Fe2(CO)4[tBuNC(H)(Me)C(O)(O)C(Me)C(H)=NtBu]

Siebenlist¹,

Frühauf²,

Vrieze³

et al. 2000

Eur. J. Inorg. Chem.

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The reaction of Fe2(CO)9 at room temperature in THF or toluene with the α‐imino ketones R1N=C(R2)–C(R3)=O (L) (R1 = alkyl, R2 = H, Me, Ph, R3 = Me, Ph) (a–k), initially results in the formation of the mononuclear chelate Fe(CO)3(α‐imino ketone) complexes 6 which can be isolated in moderate (6h) to high (6e–g) yield. Under these reaction conditions, complexes 6 subsequently react with [Fe(CO)4] fragments or dimerise, to form the dinuclear complexes Fe2(CO)6(α‐imino ketone) (7a–j) or Fe2(CO)4(L–L) (8a,b,k), respectively. The complexes 8 contain two α‐imino ketone ligands C–C coupled at the ketone carbon atoms. Complexes 8a,b react with CO at elevated temperatures to quantitatively yield Fe(CO)3(α‐imino ketone) (6a,b). This reaction can be reversed photochemically. Irradiation of a solution of 6a,b in the low‐energy band results in the reformation of 8a,b in almost quantitative yield. The extremely air‐sensitive complexes 6 and the dinuclear complexes 7 and 8 have been characterised spectroscopically (IR, UV/Vis, 1H and 13C NMR) and by elemental analysis. The solid state structures of complexes 6g and 8a have been determined by single‐crystal X‐ray diffraction. The molecular structure of 6g confirms the flat σ‐O,σ‐N chelate coordination of the α‐imino ketone. The structure of 8a consists of two metal–metal‐bonded Fe(CO)2 units, bridged by a formally 10e‐donating dianionic C–C coupled (tBu‐ADO) ligand. A mechanism for the formation of complexes 8 is discussed.

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Carbon-carbon bond formation between two .alpha.-diimines with the simultaneous formation of a metal-metal bond. X-ray structure of hexacarbonylbis[.mu.-(1-(isopropylamino)-2-(isopropylimino)ethano-N,N')]-dimolybdenum

Cited by 31 publications

References 8 publications

X-ray structure and dynamic behaviour in solution of N-methylthio-N'-2,6-dimethylphenyl).2,6-dimethyl-1,4-quinonediimine formed by the alcoholysis of [Me2 Al{2,6-Me2C6H3NS(Me)NC6H3Me2-2,6}]2

X-ray structure and dynamic behaviour in solution of N-methylthio-N'-2,6-dimethylphenyl).2,6-dimethyl-1,4-quinonediimine formed by the alcoholysis of [Me2 Al{2,6-Me2C6H3NS(Me)NC6H3Me2-2,6}]2

Metal heterodiene complexes

Preparation and Properties of Carbonyliron Complexes of 1-Aza-4-oxa-1,3-butadiene (α-Imino Ketone) – X-ray Crystal Structures of Fe(CO)3[MeNC(Ph)C(Ph)=O] and Fe2(CO)4[tBuNC(H)(Me)C(O)(O)C(Me)C(H)=NtBu]

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