Pyridine-2(1H)-thione as a bifunctional nucleophile in reaction with PdII and PtII aryl isocyanide complexes

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Pyridine-2(1H)-thione as a bifunctional nucleophile in reaction with PdII and PtII aryl isocyanide complexes. / Попов, Роман Александрович; Михердов, Александр Сергеевич; Боярский, Вадим Павлович.

In: European Journal of Inorganic Chemistry, Vol. 2022, No. 26, e202200217, 19.09.2022.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{e82f3dcdf0df44ce9853565669e1ba02,

title = "Pyridine-2(1H)-thione as a bifunctional nucleophile in reaction with PdII and PtII aryl isocyanide complexes",

abstract = "A method for obtaining C,S-cyclometalated deprotonated diaminocarbene complexes via the addition of a bifunctional N,S-nucleophile's endocyclic nitrogen atom to a coordinated isocyanide has been extended to the reactions with pyridine-2(1H)-thione. The coupling of Pd II- and Pt II-bis(arylisocyanide) complexes with pyridine-2(1H)-thione leads to the formation of mononuclear C,S-cyclometalated deprotonated diaminocarbene complexes in 90–96 % yield. The reaction proceeds via the initial coordination of the thione sulfur atom to the metal center followed by the intramolecular nucleophilic addition of the heterocyclic nitrogen atom to the metal-ligated isocyanide carbon. Using an excess of pyridine-2(1H)-thione in this reaction leads to the formation of a mono-C,S-cyclometalated complex with a pendant mercaptopyridine ligand which is involved in the reversible intramolecular nucleophilic addition of the pyridine nitrogen to the isocyano carbon. The obtained complexes were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopies, and single-crystal X-ray diffraction. ",

keywords = "Cyclometalated complexes, Isocyanides, Platinum metals complexes, Pyridine-2(1H)-thione",

author = "Попов, {Роман Александрович} and Михердов, {Александр Сергеевич} and Боярский, {Вадим Павлович}",

note = "Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = sep,

day = "19",

doi = "10.1002/ejic.202200217",

language = "English",

volume = "2022",

journal = "Berichte der deutschen chemischen Gesellschaft",

issn = "0365-9496",

publisher = "Wiley-Blackwell",

number = "26",

}

RIS

TY - JOUR

T1 - Pyridine-2(1H)-thione as a bifunctional nucleophile in reaction with PdII and PtII aryl isocyanide complexes

AU - Попов, Роман Александрович

AU - Михердов, Александр Сергеевич

AU - Боярский, Вадим Павлович

PY - 2022/9/19

Y1 - 2022/9/19

N2 - A method for obtaining C,S-cyclometalated deprotonated diaminocarbene complexes via the addition of a bifunctional N,S-nucleophile's endocyclic nitrogen atom to a coordinated isocyanide has been extended to the reactions with pyridine-2(1H)-thione. The coupling of Pd II- and Pt II-bis(arylisocyanide) complexes with pyridine-2(1H)-thione leads to the formation of mononuclear C,S-cyclometalated deprotonated diaminocarbene complexes in 90–96 % yield. The reaction proceeds via the initial coordination of the thione sulfur atom to the metal center followed by the intramolecular nucleophilic addition of the heterocyclic nitrogen atom to the metal-ligated isocyanide carbon. Using an excess of pyridine-2(1H)-thione in this reaction leads to the formation of a mono-C,S-cyclometalated complex with a pendant mercaptopyridine ligand which is involved in the reversible intramolecular nucleophilic addition of the pyridine nitrogen to the isocyano carbon. The obtained complexes were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopies, and single-crystal X-ray diffraction.

AB - A method for obtaining C,S-cyclometalated deprotonated diaminocarbene complexes via the addition of a bifunctional N,S-nucleophile's endocyclic nitrogen atom to a coordinated isocyanide has been extended to the reactions with pyridine-2(1H)-thione. The coupling of Pd II- and Pt II-bis(arylisocyanide) complexes with pyridine-2(1H)-thione leads to the formation of mononuclear C,S-cyclometalated deprotonated diaminocarbene complexes in 90–96 % yield. The reaction proceeds via the initial coordination of the thione sulfur atom to the metal center followed by the intramolecular nucleophilic addition of the heterocyclic nitrogen atom to the metal-ligated isocyanide carbon. Using an excess of pyridine-2(1H)-thione in this reaction leads to the formation of a mono-C,S-cyclometalated complex with a pendant mercaptopyridine ligand which is involved in the reversible intramolecular nucleophilic addition of the pyridine nitrogen to the isocyano carbon. The obtained complexes were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopies, and single-crystal X-ray diffraction.

KW - Cyclometalated complexes

KW - Isocyanides

KW - Platinum metals complexes

KW - Pyridine-2(1H)-thione

UR - http://www.scopus.com/inward/record.url?scp=85137252074&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/3d255662-c578-3e32-b59f-5985e6dad442/

U2 - 10.1002/ejic.202200217

DO - 10.1002/ejic.202200217

M3 - Article

VL - 2022

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 26

M1 - e202200217

ER -

ID: 97934889