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• W1965852885 endingPage "225" @default.
• W1965852885 startingPage "216" @default.
• W1965852885 abstract "The reaction of vic-dioximes with the organonitrile platinum(IV) complexes trans-[PtCl4(RCN)2] (R = Me, CH2Ph, Ph, vic-dioxime = dimethylglyoxime; R = Me, vic-dioxime = cyclohexa-, cyclohepta-, and cyclooctanedione dioximes) proceeds rapidly under relatively mild conditions and affords products of one-end addition of the dioximes to the nitrile carbon, i.e. [PtCl4(NH═C(R)ON═{spacer}═NOH)2] (1−6) (R = Me, CH2Ph, Ph, spacer = C(Me)C(Me) for dimethylglyoxime; R = Me, spacer = C{C4H8}C, C{C5H10}C, C{C6H12}C for the other dioximes), giving a novel type of metallaligand. All addition compounds were characterized by elemental analyses (C, H, N, Cl, Pt), FAB mass spectrometry, and IR and 1H, 13C{1H}, and 195Pt NMR spectroscopy. X-ray structure determination of the dimethylformamide bis-solvate [PtCl4(NH═C(Me)ON═C(Me)C(Me)═NOH)2]·2DMF (1a) disclosed its overall trans geometry with the dimethylglyoxime part in anti configuration and the amidine one-end (rather than N,N-bidentate) coordination mode of the N-donor ligands. When a mixture of cis- and trans-[PtCl4(MeCN)2] in MeCN was treated with dimethylglyoxime, the formation of, correspondingly, cis- and trans-[PtCl4(NH═C(Me)ON═C(Me)C(Me)═NOH)2] (1) was observed and cis-to-trans isomerization in DMSO-d6 solution was monitored by 1H, 2D [1H,15N] HMQC, and 195Pt NMR spectroscopies. Although performed ab initio calculations give evidence that the trans geometry is the favorable one for the iminoacylated species [PtCl4(ligand)2], the platinum(IV) complex [PtCl4(NH═C(Me)ON═C{C4H8}C═NOH)2] (4) was isolated exclusively in cis configuration with the two metallaligand “arms” held together by intramolecular hydrogen bonding between the two peripheral OH groups, as it was proved by single-crystal X-ray diffractometry. The classic substitution products, e.g. [PtCl2(N,N-dioximato)2] (12−15), are formed in the addition reaction as only byproducts in minor yield; two of them, [PtCl2(C7H11N2O2)2] (14) and [PtCl2(C8H13N2O2)2] (15), were structurally characterized. Complexes (12−15) were also prepared by reaction of the vic-dioximes with [PtCl4L(Me2SO)] (L = Me2SO, MeCN), but monoximes (Me2C═NOH, {C4H8}C═NOH, {C5H10}C═NOH, PhC(H)═NOH, (OH)C6H4C(H)═NOH) react differently adding to [PtCl4(MeCN)(Me2SO)] to give the corresponding iminoacylated products [PtCl4(NH═C(Me)ON═CRR‘)(Me2SO)] (7−11)." @default.
• W1965852885 created "2016-06-24" @default.
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• W1965852885 date "2000-01-05" @default.
• W1965852885 modified "2023-09-23" @default.
• W1965852885 title "Iminoacylation. 3. Formation of Platinum(IV)-Based Metallaligands Due to Facile One-End Addition of <i>v</i><i>ic</i>-Dioximes to Coordinated Organonitriles^1-3" @default.
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• W1965852885 doi "https://doi.org/10.1021/ic990552m" @default.
• W1965852885 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/11272528" @default.
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