Theoretical study of Re(IV) and Ru(II) bis-isocyanide complexes and their reactivity in cycloaddition reactions with nitrones

Novikov, Alexander S.; Kuznetsov, Maxim L.

doi:10.1016/j.ica.2011.08.016

Cited by 51 publications

(17 citation statements)

References 68 publications

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“…This integrated approach has been already used by one of us [45] and by our colleagues [24] for studies of rhenium [45], ruthenium [45], palladium [24], and platinum [24] species. We used all these methods to study the nature of the coordination Cu-C bonds and the formal triple C"N bonds in 1.…”

Section: Nature Of the Coordination Cu-c Bonds And The Formal Triple mentioning

confidence: 99%

Tris-isocyanide copper(I) complexes: Synthetic, structural, and theoretical study

Melekhova

Novikov

Luzyanin

et al. 2015

Inorganica Chimica Acta

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Section: Nature Of the Coordination Cu-c Bonds And The Formal Triple mentioning

confidence: 99%

Tris-isocyanide copper(I) complexes: Synthetic, structural, and theoretical study

Melekhova

Novikov

Luzyanin

et al. 2015

Inorganica Chimica Acta

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“…As a result of the interaction between K 2 [PtCl 4 ] and C≡NMe and the following addition of hydrazine, the first complex of a heteroatom-stabilized carbene was obtained [ 46 , 47 , 48 , 49 ]. Since that time, the metal-mediated addition of the monofunctional O- [ 50 , 51 , 52 , 53 , 54 ], N- [ 34 , 35 , 36 , 37 , 41 , 43 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 ], and other [ 71 , 72 , 73 , 74 , 75 , 76 , 77 , 78 ] nucleophiles as well as bifunctional nucleophiles [ 27 , 34 , 53 , 62 , 64 , 79 , 80 , 81 , 82 , …”

Section: Introductionmentioning

confidence: 99%

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Kuznetsov

Kukushkin

2017

Molecules

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Despite the long history of the investigation of nucleophilic addition to metal-bound isocyanides, some important aspects of the reaction mechanism remain unclear even for the simplest systems. In this work, the addition of the sp3-N, sp2-N, and mixed sp2/sp3-N nucleophiles (i.e., HNMe2, HN=CPh2, and H2N–N=CPh2, respectively) to isocyanides C≡NR coordinated to the platinum(II) centers in the complexes cis-[Pt(C≡NCy)(2-pyz)(dppe)]+ (2-pyz = 2-pyrazyl, dmpe = Me2PCH2CH2PMe2) and cis-[PtCl2(C≡NXyl)(C≡NMe)] was studied in detail by theoretical (DFT) methods. The mechanism of these reactions is stepwise associative rather than concerted and it includes the addition of a nucleophile to the isocyanide C atom, deprotonation of the nucleophilic moiety in the resulting intermediate, and protonation of the isocyanide N atom to give the final product. The calculated activation energy (ΔG≠) of all reactions is in the range of 19.8–22.4 kcal/mol.

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“…Previously [ 94 , 95 ], some of us demonstrated that the coordination of isocyanides to a metal center plays a tremendous role in the activation of C≡NR toward NA. Therefore, in this section we discuss results of the theoretical analysis of the coordination Pd–C bond nature in the starting Pd isocyanide complex 1 , in two isomeric products Z - P1 , and Z - P2 and in two rate-determining transition states leading to these products, TS6 and TS14 .…”

Section: Resultsmentioning

confidence: 99%

Reaction between Indazole and Pd-Bound Isocyanides—A Theoretical Mechanistic Study

et al. 2018

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The mechanism of the addition of indazole (Ind)—a bifunctional aromatic N,NH-nucleophile—to cyclohexyl isocyanide coordinated to the palladium(II) center in the model complex cis-[PdCl2(CNMe)(CNCy)] (1) to give the corresponding aminocarbene ligand was investigated in detail by theoretical (DFT) methods. The most plausible mechanism of this reaction is that of the associative type involving nucleophilic attack of Ind by its unprotonated N atom at the isocyanide carbon atom followed by the stepwise proton transfer from the nucleophile molecule to the isocyanide N atom via deprotonation/protonation steps. Two reaction channels based on two tautomeric forms of indazole were found. The channel leading to the experimentally isolated aminocarbene product is based on the less stable tautomeric form. Another channel based on the more stable tautomer of Ind is slightly kinetically more favorable but it is endergonic. Thus, the regioselectivity of this reaction is thermodynamically rather than kinetically driven. The bonding situation in key species was analyzed.

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Theoretical study of Re(IV) and Ru(II) bis-isocyanide complexes and their reactivity in cycloaddition reactions with nitrones

Cited by 51 publications

References 68 publications

Tris-isocyanide copper(I) complexes: Synthetic, structural, and theoretical study

Tris-isocyanide copper(I) complexes: Synthetic, structural, and theoretical study

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Reaction between Indazole and Pd-Bound Isocyanides—A Theoretical Mechanistic Study

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