Theoretical study of nucleophilic addition of amines to organic nitriles

Kuznetsov, Maxim L.; Bokach, Nadezhda A.; Kharlampidi, D. D.; Medvedev, Yu. N.; Kukushkin, Vadim Yu.; Dementiev, A. I.

doi:10.1134/s1070363210030151

Cited by 10 publications

(5 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this part, the plausible mechanisms of the formation of complexes 3 (methyl derivative 3c ) are discussed. Taking into account the previous experimental ,, and theoretical data on the reactions of addition of various protic nucleophiles (H 2 O, ROH, NH 3 , RNH 2 , RR′NH, NR 2 OH, RR′CNOH, etc.) to metal-bound nitriles, it seems to be a good assumption that the reaction starts with the nucleophilic addition (NA) of 1,3-diiminoisoindoline 2 to one of the nitrile ligands of complex trans -[PtCl 2 (NCR) 2 ] to give imino-complexes I – III followed by the first cyclization to IV (with HCl elimination) and then by the second nucleophilic addition/cyclization affording the final product 3 (Scheme , Pathway A).…”

Section: Resultsmentioning

confidence: 99%

Pt^II-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

et al. 2012

View full text Add to dashboard Cite

Treatment of trans-[PtCl(2)(NCR)(2)] (1; R = Et (1a), Ph (1b)) with 1,3-diiminoisoindoline (2) gives access to the corresponding symmetrical (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato)Pt(II) complexes [PtCl{NH═C(R)N═C(C(6)H(4))NC═NC(R)═NH}] (3). The reactions of 1 with one equivalent of 1,1,3,3-tetramethylguanidine (4), 1,3-diphenylguanidine (6), or acetone oxime (8) leads to the formation of mixed asymmetrical Pt(II) complexes trans-[PtCl(2){NH═C(R)N═C(NMe(2))(2)}(NCR)] (5), [PtCl{NH═C(R)NC(NHPh)═NPh}(NCR)] (7), or trans-[PtCl(2){NH═C(Ph)ON═CMe(2)}(NCPh)] (9), respectively, as a result of nucleophilic addition to one of the nitrile ligands in 1. Treatment of 5, 7, and 9 with one equivalent of 2 leads to complexes 3. The complexes were characterized by IR, (1)H, (13)C{(1)H}, and (195)Pt NMR (for 3) spectroscopies, ESI(+)-MS, elemental analyses, and X-ray diffraction (for 3). Complex 3a has an asymmetric unit with five independent Pt molecules of the same chemical composition and two molecules of water, resulting in a total of 40 molecules of the complex and sixteen guest water molecules per unit cell. Theoretical calculations revealed that the most plausible mechanism of formation of complexes 3 includes stepwise nucleophilic addition of 2 to one of the nitrile ligands in 1, a first cyclization upon formation of the Pt-N bond and elimination of HCl, and a second nucleophilic addition/cyclization.

show abstract

Section: Resultsmentioning

confidence: 99%

Pt^II-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

et al. 2012

View full text Add to dashboard Cite

show abstract

“…This is due to a flow of electrons from the ligand leading to a shorter and strong bond. Natural bond orbital, NBO charge is a measure of π‐electron delocalization and shows the degree of the aromaticity of the atom aromatic rings . The flow of electrons from phenyl rings of N triazine to metal causing increased electron density on the metal center, resulting in less positive NBO charges on Fe 2+ .…”

Section: Resultsmentioning

confidence: 99%

Substitution Kinetics of [Fe(PDT/PPDT)_n(phen)_m]²⁺(n≠m;n,m= 1,2) with 2,2′-Bipyridine, 1,10-Phenanthroline, and 2,2′,6,2″-Terpyridine

Bellam

Jaganyi

2017

Int. J. Chem. Kinet.

View full text Add to dashboard Cite

The triazines 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PDT), 3-(4-phenyl-2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PPDT), and 1,10-phenanthroline (phen) were coordinated to the Fe 2+ ion to form Fe(PDT) 2 (phen) 2+ (1), Fe(PPDT) 2 (phen) 2+ (2), Fe(PDT)(phen) 2+ 2 , (3) and Fe(PPDT)(phen) 2+ 2 (4). The complexes were synthesized and characterized by mass spectroscopy and elemental analysis. The rate of substitution of these complexes by 2,2 -bipyridine (bpy), 1,10-phenanthroline (phen), and 2,2 ,6,2 -terpyridine (terpy) was studied in a sodium acetate-acetic acid buffers over the range 3.6-5.6 at 25, 35, and 45°C under pseudo-first-order conditions. The reactions are first order with respect to the concentration of the complexes. The reaction rates increase with increasing [bpy/phen/terpy] and pH, whereas ionic strength has no influence on the rate of reaction. Plots of k obs versus [bpy/phen/terpy] and 1/[H + ] are linear with positive slopes and significant y-intercepts. This indicates that the reactions proceed by both dissociative as well as associative pathways for which the associative pathway predominates the substitution kinetics. Observed temperature-depended rate constants at the three temperatures at which substitution reactions were studied together with the protonation constants of the substituting ligands (phen, bpy, terpy) were used to evaluate the specific rate constants (k 1 and k 2 ) and thermodynamic parameters (E a , H # , S # , and G # ). The reactivity order of the four complexes depends on the phenyl groups present on the triazine (PDT/PPDT)Correspondence to: R. Bellam; e-mail: rajeshchowdarybellam@ gmail.com.Supporting Information is available in the online issue at www.wileyonlinelibrary.com.C 2017 Wiley Periodicals, Inc. SUBSTITUTION KINETICS OF [Femolecule. The π -electrons on phenyl rings stabilizes the charge on the metal center by inductive donation of electrons toward the metal center resulting in a decrease in reactivity of the complex, and the order is 1 < 2 < 3 < 4. The rate of substitution is also influenced by the basicity of the incoming ligand (bpy/phen/terpy), and it decreased in the order: phen > terpy > bpy. Higher rate constants, low E a values , and more negative entropy of activation (− S # ) values were observed for the associative path, revealing that substitution reactions at the octahedral iron(II) complexes by bpy, phen, and terpy occur predominantly by the associative mechanism. Density functional theory calculations support the interpretations.

show abstract

“…The latter may isomerize to the corresponding Z-isomer depending on the nature of the nucleophile (Scheme 3). [46,47] Notably, for the addition of alcohols to coordinated nitriles, the first addition product is the Z isomer. [48] Reactions of Pt II nitriles with primary amines…”

Section: Chemistry Synthesismentioning

confidence: 99%

Chemistry and Biological Activity of Platinum Amidine Complexes

et al. 2011

View full text Add to dashboard Cite

Platinum amidine complexes represent a new class of potential antitumor drugs that contain the imino moiety HN=C(sp(2)) bonded to the platinum center. They can be related to the iminoether derivatives, which were recently shown to be the first Pt(II) compounds with a trans configuration endowed with anticancer activity. The chemical and biological properties of platinum amidine complexes, and more generally of platinum imino derivatives, can be rationally modified through suitable synthetic procedures with the aim of improving their cytotoxicity and antitumor activity. The addition of protic nucleophiles to nitriles coordinated to platinum in various oxidation states can offer a wide variety of complexes with chemical, structural, and physical properties specifically tuned for a more efficacious biological response.

show abstract

Theoretical study of nucleophilic addition of amines to organic nitriles

Cited by 10 publications

References 41 publications

Pt^II-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

Pt^II-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

Substitution Kinetics of [Fe(PDT/PPDT)_n(phen)_m]²⁺(n≠m;n,m= 1,2) with 2,2′-Bipyridine, 1,10-Phenanthroline, and 2,2′,6,2″-Terpyridine

Chemistry and Biological Activity of Platinum Amidine Complexes

Contact Info

Product

Resources

About

Theoretical study of nucleophilic addition of amines to organic nitriles

Cited by 10 publications

References 41 publications

PtII-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

PtII-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

Substitution Kinetics of [Fe(PDT/PPDT)n(phen)m]2+(n≠m;n,m= 1,2) with 2,2′-Bipyridine, 1,10-Phenanthroline, and 2,2′,6,2″-Terpyridine

Chemistry and Biological Activity of Platinum Amidine Complexes

Contact Info

Product

Resources

About

Pt^II-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

Pt^II-Mediated Imine–Nitrile Coupling Leading to Symmetrical (1,3,5,7,9-Pentaazanona-1,3,6,8-tetraenato)Pt(II) Complexes Containing the Incorporated 1,3-Diiminoisoindoline Moiety

Substitution Kinetics of [Fe(PDT/PPDT)_n(phen)_m]²⁺(n≠m;n,m= 1,2) with 2,2′-Bipyridine, 1,10-Phenanthroline, and 2,2′,6,2″-Terpyridine