The chemistry and structure of Chugaev's salt and related compounds containing a cyclic carbene ligand

Rouschias, G.; Shaw, Bernard L.

doi:10.1039/j19710002097

Cited by 37 publications

(23 citation statements)

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“…It has been previously demonstrated5 that the ligands in complexes such as la (M = Pt, Pd) are acidic and that a proton may be removed from one of the interior chelate ring In (CD3)2SO. 6 In CD3N02. = In (CD3)2CO.…”

Section: Resultsmentioning

confidence: 99%

Platinum and palladium complexes formed by chelative addition of amines to isocyanides

Balch¹,

Parks²

1974

J. Am. Chem. Soc.

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The addition of amines to coordinated isocyanides has been explored as a method of preparing new chelating ligands. The reaction of amidines and 2-aminopyridine with Pt(CNCH8)42+ produces complexes of the type (chelate)Pt(CNCH3)22+'+ containing bidentate ligands which utilize one imine nitrogen donor and one trigonal carbon donor. Biacetyldihydrazone reacts with M(CNCH3)42+ (M = Pd, Pt) to produce a bidentate ligand which contains two trigonal carbon donors, one of which is incorporated into an imidazole ring. The addition of 2,6diaminopyridine to M(CNCH3)42+ produces a tridentate ligand with one pyridine nitrogen donor and two trigonal carbon donors. These new complexes have been isolated and characterized by elemental analysis, conductivities,

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Section: Resultsmentioning

confidence: 99%

Platinum and palladium complexes formed by chelative addition of amines to isocyanides

Balch¹,

Parks²

1974

J. Am. Chem. Soc.

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“…The first metal-mediated reaction of C≡NR species was observed more than 100 years ago by Tschugajeff (Chugaev) and Skanawy-Grigorjewa [ 44 , 45 ]. 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 ,…”

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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“…Pt ii complexes featuring Chugaev-type 67,71–76,105–107 chelating bis-ACD ligands 54 and 55 were assembled via the template reaction of t BuNC, excess hydrazine hydrate, and aqueous K 2 [PtCl 4 ]; separation was achieved by fractional recrystallisation (Scheme 7, Route A). 108 Through this reaction, two coordinated t BuNCs reacted with hydrazine to yield a deprotonated chelating dicarbene ligand in 54 and 55 .…”

Section: Luminescent [M]-adc Complexesmentioning

confidence: 99%

Tuning the luminescence of transition metal complexes with acyclic diaminocarbene ligands

Kinzhalov

Grachova

Luzyanin

2022

Inorg. Chem. Front.

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The chemistry and structure of Chugaev's salt and related compounds containing a cyclic carbene ligand

Cited by 37 publications

References 0 publications

Platinum and palladium complexes formed by chelative addition of amines to isocyanides

Platinum and palladium complexes formed by chelative addition of amines to isocyanides

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

Tuning the luminescence of transition metal complexes with acyclic diaminocarbene ligands

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