Synthesis of [Ag(NHCMe2)2]ClO4and Its Use as a Source of Acetimine. 1. Synthesis of the First Acetimine Rhodium Complexes and the First Crystal Structure of a Diacetonamine Complex

Vicente, José; Chicote, Mariá‐Teresa; Guerrero, Rita; Vicente-Hernandez, Inmaculada; Jones, Peter G.

doi:10.1021/ic035002+

Cited by 13 publications

(25 citation statements)

References 44 publications

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“…Ligands (tmeda, bpy, tbbp, RNC) and reagents (carbodiimides, isothiocyanates, nitriles, cyanamides, maleates, fumarates, 1,1‐dimethylallene) were purchased and used as received. [Pd 2 (dba) 3 ]⋅dba (“Pd(dba) 2 ”; dba=dibenzylideneacetone)93 and [Ag(NHCMe 2 ) 2 ]ClO 4 94 were prepared as reported. We have described elsewhere the synthesis of complexes 1 aOH ,12 1 bOH ,25 1 cOH ,12 1 aNH ,82 1 bCHO ,17 1 bCN 17 2 bOH ,31 3 bOH ,31 5 bOH ,31 12 aOH ,30 16 aOH ,30 and 19 aOH ,30 and the crystal structures of 2 bOH ,31 5 bOH ,31 12 aOH ,30 16 aOH ,30 and 19 aOH 30.…”

Section: Methodsmentioning

confidence: 99%

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

Vicente

Abad

López-Sáez

et al. 2009

Chemistry A European J

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Complexes [Pd(C(6)H(3)XH-2-R'-5)Y(N;N)] (X=O, NH; Y=Br, I; R'=H, NO(2); N;N=N,N,N',N'-tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy)) react with RN=C=E (E=NR, S) or RC identical withN (R=alkyl, aryl, NR''(2)) and TlOTf (OTf=CF(3)SO(3)) to give, respectively, 1) products of the insertion of the C=E group into the C--Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{kappa(2)-X,E-(XC(6)H(3){EC(NHR)}-2-R'-4)}(N;N)]OTf or [Pd(kappa(2)-X,N-{ZC(6)H(3)(NH=CR)-2-R'-4})(N;N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{kappa(2)-C,N-(C(6)H(4){OC(NR)}NHR-2)}(bpy)]OTf; or 2) products of the insertion of the C identical withN group to Pd and N-protonation, [Pd(kappa(2)-X,N-{XC(6)H(3)(NH=CR)-2-R'-4})(N;N)]OTf.

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Section: Methodsmentioning

confidence: 99%

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

Vicente

Abad

López-Sáez

et al. 2009

Chemistry A European J

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“…Although the metal-mediated condensation of NH 2 OH and carbonyl compounds has been illustrated by only two examples, relevant metal-involving reactions between NH 3 and R 2 CO leading to imines − and between N 2 H 4 and R 2 CO leading to hydrazones , are more abundant.…”

Section: Metal-mediated Generation Of Oximesmentioning

confidence: 99%

Metal-Involving Synthesis and Reactions of Oximes

et al. 2017

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This review classifies and summarizes the past 10-15 years of advancements in the field of metal-involving (i.e., metal-mediated and metal-catalyzed) reactions of oximes. These reactions are diverse in nature and have been employed for syntheses of oxime-based metal complexes and cage-compounds, oxime functionalizations, and the preparation of new classes of organic species, in particular, a wide variety of heterocyclic systems spanning small 3-membered ring systems to macroheterocycles. This consideration gives a general outlook of reaction routes, mechanisms, and driving forces and underlines the potential of metal-involving conversions of oxime species for application in various fields of chemistry and draws attention to the emerging putative targets.

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“…2 Its difficult synthesis 3,4 and handling may account for the scarcity of acetimino complexes reported so far, 5-8 none of which has been obtained using acetimine itself. We have described the syntheses of [Au(NHdCMe 2 )PPh 3 ]ClO 4 8 and [Ag(NHd CMe 2 ) 2 ]ClO 4 9 and their use for preparing the first acetimino Rh(I) 9 and Rh(III) 10 complexes; an interesting coupling process between two acetimino ligands was found to occur at a Rh(III) center to give a 2-methyl-2-amino-4-iminopentano ligand. 10,11 While this paper was being written, a paper by Natile et al has appeared 12 describing the synthesis and in vitro antitumor activity of the first acetimino complexes of platinum, namely, the cis and trans isomers of [PtX 2 (NHd CMe 2 ) 2 ] and [PtX 2 (NHdCMe 2 )(NH 3 )] (X ) Cl, I), in which the Me 2 CdNH ligands form from the reaction of coordinated ammonia with acetone in the presence of KOH.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Acetimino Complexes of Pt(II) and Pt(IV) and the First Heteronuclear μ-Acetimido Complexes

et al. 2006

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The reactions of [Ag(NH=CMe2)2]ClO4 with cis-[PtCl2L2] in a 1:1 molar ratio give cis-[PtCl(NH=CMe2)(PPh3)2]ClO4 (1cis) or cis-[PtCl(NH=CMe2)2(dmso)]ClO4 (2), and in 2:1 molar ratio, they produce [Pt(NH=CMe2)2L2](ClO4)2 [L = PPh3 (3), L2= tbbpy = 4,4'-di-tert-butyl-2,2'-dipyridyl (4)]. Complex 2 reacts with PPh3 (1:2) to give trans-[PtCl(NH=CMe2)(PPh3)2]ClO(4) (1trans). The two-step reaction of cis-[PtCl2(dmso)2], [Au(NH=CMe2)(PPh3)]ClO4, and PPh3 (1:1:1) gives [SP-4-3]-[PtCl(NH=CMe2)(dmso)(PPh3)]ClO4 (5). The reactions of complexes 2 and 4 with PhICl2 give the Pt(IV) derivatives [OC-6-13]-[PtCl3(NH=CMe2)(2)(dmso)]ClO4 (6) and [OC-6-13]-[PtCl2(NH=CMe2)2(dtbbpy)](ClO4)2 (7), respectively. Complexes 1cis and 1trans react with NaH and [AuCl(PPh3)] (1:10:1.2) to give cis- and trans-[PtCl{mu-N(AuPPh3)=CMe2}(PPh3)2]ClO4 (8cis and 8trans), respectively. The crystal structures of 4.0.5Et2O.0.5Me2CO and 6 have been determined; both exhibit pseudosymmetry.

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Synthesis of [Ag(NHCMe₂)₂]ClO₄and Its Use as a Source of Acetimine. 1. Synthesis of the First Acetimine Rhodium Complexes and the First Crystal Structure of a Diacetonamine Complex

Cited by 13 publications

References 44 publications

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

Metal-Involving Synthesis and Reactions of Oximes

Synthesis of Acetimino Complexes of Pt(II) and Pt(IV) and the First Heteronuclear μ-Acetimido Complexes

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