Unusual Reactivity Mode of Coordinated Oximes:  Platinum(IV)-Assisted Ring Closure by Reaction with Acetone

Kukushkin, Vadim Yu.; Belsky, V. K.; Tudela, David

doi:10.1021/ic950351s

Cited by 26 publications

(16 citation statements)

References 37 publications

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“…Two possible formulations may be envisaged for this product, namely an η 2 -acetone adduct of a monohapto W−iminoacyl H or a metallacyclic structure I derived from a [3 + 2] cycloaddition of the W−C(N- i -Pr)Me fragment to a molecule of acetone. Precedent for the latter possibility can be found in previous work by Werner and co-workers. , In order to unambiguously characterize this material, X-ray studies were attempted. While crystals of 8cad suitable for this determination could not be obtained, the related complex 9cad , isolated after the analogous reaction of CpWMe(CO) 2 (CNMe) ( 9al ) in acetone, readily provided single crystals.…”

Section: Resultsmentioning

confidence: 99%

Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

et al. 1997

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The metalate salts Y+[Cp‘M(CO)2(CNR)]- (Y = Na, K; M = Mo, W; CNR = alkylisocyanide), in the presence of the soft electrophile MeI, experience alkylation at the metal center to afford methyl complexes of composition Cp‘MMe(CO)2(CNR). The kinetic stability of these alkyls toward rearrangement to the η2-iminoacyls Cp‘M(η2-C(NR)Me)(CO)2 or the η3-1-azaallyls Cp‘M(η3-CH2C(H)NR)(CO)2 has been found to depend markedly upon the nature of the metal, the isocyanide R substituent, and the solvent used. With respect to the latter, solvents with efficient Lewis basic capabilities (e.g., pyridine or acetonitrile) favor η2-iminoacyl formation while those which are poor donors (benzene, diethyl ether) preferentially generate the η3-azaallyls. The use of acetone as the solvent in reactions involving the Me−W−CNR complexes has allowed the isolation of metallacyclic structures of composition Cp‘W(η2(C,O)-C(Me)N(R)C(Me)2O)(CO)2, formally as the result of a [3 + 2] cycloaddition of a W−η1-C(NR)Me residue to a molecule of acetone. Two of the newly reported complexes, namely the η3-1-azaallyl CpMo(η3-CH2CHN-t-Bu)(CO)2 (1az) and the heterometallacycle CpW(η2(C,O)-C(Me)N(Me)C(Me)2O)(CO)2 (9cad) have been structurally characterized by X-ray crystallography.

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Section: Resultsmentioning

confidence: 99%

Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

et al. 1997

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“…Similar processes involving metal complexes are also known although scarce. 14,15 Metal-mediated iminoacylation of oximes is an even lesser explored area, and only one example of such a reaction has been published so far. Thus, Grigg et al 16 and concurrently Zerbib et al 17 reported one-pot multistep processes between oxovanadium(IV) aldoxime and ketoxime complexes, for example [VO{C 6 H 4 (O)CHdNOH} 2 ], under treatment with acetonitrile.…”

Section: Introductionmentioning

confidence: 99%

“…As far as addition reactions of oximes are concerned, it is well-documented that oximes are ambidentate nucleophiles and their N - or O -alkylation, acylation, and arylation have been extensively studied and reviewed in organic chemistry. Similar processes involving metal complexes are also known although scarce. , Metal-mediated iminoacylation of oximes is an even lesser explored area, and only one example of such a reaction has been published so far. Thus, Grigg et al and concurrently Zerbib et al reported one-pot multistep processes between oxovanadium(IV) aldoxime and ketoxime complexes, for example [VO{C 6 H 4 (O)CHNOH} 2 ], under treatment with acetonitrile.…”

Section: Introductionmentioning

confidence: 99%

Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles

et al. 1998

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The metal-mediated iminoacylation reaction of ketoximes or aldoximes upon treatment with the organonitrile platinum(IV) complexes trans-[PtCl(4)(RCN)(2)] proceeds under relatively mild conditions in acetonitrile (R = Me) or in chloroform (R = CH(2)Ph, Ph) to give trans-[PtCl(4)(NH=C(R)ON=CR(1)R(2))(2)] (R(1) = R(2) = Me; R(1)R(2) = C(4)H(8), R(1)R(2) = C(5)H(10), R(1)R(2) = (H)Ph, R(1)R(2) = (H)C(6)H(4)(OH)-o; 1-14) in 90-95% yield. All these compounds were characterized by elemental analyses (C, H, N, Cl, Pt), FAB mass spectrometry, and IR and (1)H, (13)C{(1)H}, and (195)Pt NMR spectroscopies. X-ray structure determinations of [PtCl(4)(NH=C(Me)ON=CMe(2))(2)] (1) and [PtCl(4){NH=C(Me)ON=C(C(5)H(10))}(2)] (3) disclosed their overall trans-configuration and the amidine one-end rather than N,N-bidentate coordination mode of the N-donor ligands. The iminoacyl species are in E-conformation which is held by a rather weak N-H.N hydrogen bond between the amidine =NH atom and the oxime nitrogen with the following observed distances and angles for 1 and [3]: N(1).N(2), and N(1)-H, N(1)H.N(2) are 2.605 [2.592], 0.74 [0.71], and 2.20 [2.25] Å; N(1)-H.N(2) is 115 degrees [111 degrees ]. No evidence of the Z-conformation in solution was obtained by NMR spectroscopy. Compounds trans-[PtCl(4)(NH=C(R)ON=CR(1)R(2))(2)] are unexpectedly stable toward hydrolysis both in the solid state and in solutions.

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“…Previously, we have observed that the same platinum(II) complexes trans- [PtCl 2 (RR‘CNOH) 2 ], where R = R‘ = Me and RR‘ = (CH 2 ) 4 and (CH 2 ) 5 , react with MCPBA in Me 2 CO to give the platinum(IV) compounds [PtCl 2 (OCMe 2 ONCRR‘) 2 ] without change in the oxidation state of the oxime N atom …”

Section: Introductionmentioning

confidence: 99%

Reactivity oftrans-[PtX₂(ketoxime)₂] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

et al. 1996

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The platinum(II) compounds trans-[PtX(2)(RR'C=NOH)(2)] [X = Cl, R = R' = Me, RR' = (CH(2))(4), (CH(2))(5); X = Br, R = R' = Me] react with m-chloroperoxybenzoic acid (MCPBA) in dimethylformamide to give the platinum(II) complexes [PtX(2){N(=O)CRR'ONCRR'}] containing coordinated nitrosoalkane ligands. The complexes [PtX(2){N(=O)CRR'ONCRR'}] were characterized by elemental analysis, EI-MS, IR, electronic absorption, and (1)H NMR spectroscopy; X-ray structure analysis was performed for [PtCl(2){N(=O)CC(5)H(10)ONCC(5)H(10)}]. The latter compound crystallizes in the triclinic P&onemacr; space group with a = 9.214(2) Å, b = 9.577(2) Å, c = 10.367(2) Å, alpha = 109.14(2) degrees, beta = 91.87(2) degrees, gamma = 115.62(2) degrees, V = 762.8(3) Å(3), Z = 2, and rho(calcd) = 2.135 g cm(-)(3). The reaction between trans-[PtX(2)(RR'C=NOH)(2)] and MCPBA displays a solvent dependence: interaction of these reagents in ketones, R(1)R(2)C=O, yields the platinum(IV) chelates [PtX(2)(OCR(1)R(2)ON=CRR')(2)], while the oxidation state of the oxime N atom remains unchanged. Heating [PtCl(2)(OCR(1)R(2)ON=CRR')(2)] in DMF or in DMF-d(7) at 100 degrees C leads to the extrusion of R(1)R(2)C=O and the formation of [PtCl(2){N(=O)CRR'ONCRR'}].

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Unusual Reactivity Mode of Coordinated Oximes: Platinum(IV)-Assisted Ring Closure by Reaction with Acetone

Cited by 26 publications

References 37 publications

Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles

Reactivity oftrans-[PtX₂(ketoxime)₂] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

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Unusual Reactivity Mode of Coordinated Oximes: Platinum(IV)-Assisted Ring Closure by Reaction with Acetone

Cited by 26 publications

References 37 publications

Formation of η2-Iminoacyls, η3-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

Formation of η2-Iminoacyls, η3-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

Iminoacylation. 1. Addition of Ketoximes or Aldoximes to Platinum(IV)-Bound Organonitriles

Reactivity oftrans-[PtX2(ketoxime)2] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction

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Product

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Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

Formation of η²-Iminoacyls, η³-Azaallyls, and Heterometallacycles during the Rearrangements of Methyl Complexes of Molybdenum and Tungsten Containing Isocyanide Ligands

Reactivity oftrans-[PtX₂(ketoxime)₂] Complexes towardm-Chloroperoxybenzoic Acid: An Efficient Route to Coordinated Nitrosoalkanes and Solvent Dependence of the Reaction