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Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides : Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile. / Kinzhalov, Mikhail A.; Timofeeva, Svetlana A.; Luzyanin, Konstantin V.; Boyarskiy, Vadim P.; Yakimanskiy, Anton A.; Haukka, Matti; Kukushkin, Vadim Yu.

In: Organometallics, Vol. 35, No. 2, 25.01.2016, p. 218-228.

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

Harvard

Kinzhalov, MA, Timofeeva, SA, Luzyanin, KV, Boyarskiy, VP, Yakimanskiy, AA, Haukka, M & Kukushkin, VY 2016, 'Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides: Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile', Organometallics, vol. 35, no. 2, pp. 218-228. https://doi.org/10.1021/acs.organomet.5b00936

APA

Kinzhalov, M. A., Timofeeva, S. A., Luzyanin, K. V., Boyarskiy, V. P., Yakimanskiy, A. A., Haukka, M., & Kukushkin, V. Y. (2016). Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides: Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile. Organometallics, 35(2), 218-228. https://doi.org/10.1021/acs.organomet.5b00936

Vancouver

Kinzhalov MA, Timofeeva SA, Luzyanin KV, Boyarskiy VP, Yakimanskiy AA, Haukka M et al. Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides: Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile. Organometallics. 2016 Jan 25;35(2):218-228. https://doi.org/10.1021/acs.organomet.5b00936

Author

Kinzhalov, Mikhail A. ; Timofeeva, Svetlana A. ; Luzyanin, Konstantin V. ; Boyarskiy, Vadim P. ; Yakimanskiy, Anton A. ; Haukka, Matti ; Kukushkin, Vadim Yu. / Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides : Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile. In: Organometallics. 2016 ; Vol. 35, No. 2. pp. 218-228.

BibTeX

@article{5a7eb7c310d94a5e9532806d9a21a193,
title = "Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides: Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile",
abstract = "Coupling of the palladium-bis(isocyanide) complexes cis-[PdCl2(CNR)2] (R = 2,6-Me2C6H3 1, 2-Cl-6-MeC6H3 2) with benzene-1,3-diamine (BDA1) leads to the diaminocarbene species cis-[PdCl2(CNR){C(NHR)=NH(1,3-C6H4NH2)}] (5 and 6, respectively). In this reaction, BDA1 behaves as a monofunctional nucleophile that adds to one of the RNC ligands by one amino group. By contrast, the reaction of 1 and 2 with benzene-1,4-diamine (BDA2) involves both amino functionalities of the diamine and leads to the binuclear species [cis-PdCl2(CNR){ΜC(NHR)=NH(1,4-C6H4)NH=C(NHR)}-(cis)-PdCl2(CNR)] (6 and 7) featuring two 1,4-bifunctional diaminocarbene ligands. The reaction of cis-[PdCl2(CNR)2] (R = cyclohexyl 3) with either BDA1 or BDA2 does not afford any isolable carbene derivatives. The most versatile chemistry was observed when 1-3 were treated with benzene-1,2-diamine (BDA3) and the relevant substituted 1,2-diamines, viz., 4,5-dimethylbenzene-1,2-diamine (BDA4) and 4,5-dichlorobenzene-1,2-diamine (BDA5). The addition of these diamines brings about the formation of the monocarbene cationic complexes cis-[PdCl(CNR){C(NHR)=NHC6H2X2NH2}]Cl (X = H, Me, Cl) (8-16), the Chugaev-type C,C-bound bis-carbenes cis-[PdCl2{C(NHR)=NHC6H2X2NH=C(NHR)}] (17, 18), and the bis(C,N-chelated)carbene complexes cis-[Pd{C(NHR)=NHC6H2X2NH2}2]Cl2 (19-24). All prepared complexes (with the exception of 17 and 18) were isolated as colorless or pale yellow solids and characterized by elemental analyses (C, H, N), HRESI±-MS, IR, 1H and 13C{1H} NMR spectroscopies, and 4, 7, 13, 16, and 24 by X-ray diffraction. Complexes 17 and 18 were characterized by HRESI±-MS and IR spectroscopy, and their structures were established by X-ray crystallography.",
author = "Kinzhalov, {Mikhail A.} and Timofeeva, {Svetlana A.} and Luzyanin, {Konstantin V.} and Boyarskiy, {Vadim P.} and Yakimanskiy, {Anton A.} and Matti Haukka and Kukushkin, {Vadim Yu}",
note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society. Copyright: Copyright 2016 Elsevier B.V., All rights reserved.",
year = "2016",
month = jan,
day = "25",
doi = "10.1021/acs.organomet.5b00936",
language = "English",
volume = "35",
pages = "218--228",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "2",

}

RIS

TY - JOUR

T1 - Palladium(II)-Mediated Addition of Benzenediamines to Isocyanides

T2 - Generation of Three Types of Diaminocarbene Ligands Depending on the Isomeric Structure of the Nucleophile

AU - Kinzhalov, Mikhail A.

AU - Timofeeva, Svetlana A.

AU - Luzyanin, Konstantin V.

AU - Boyarskiy, Vadim P.

AU - Yakimanskiy, Anton A.

AU - Haukka, Matti

AU - Kukushkin, Vadim Yu

N1 - Publisher Copyright: © 2016 American Chemical Society. Copyright: Copyright 2016 Elsevier B.V., All rights reserved.

PY - 2016/1/25

Y1 - 2016/1/25

N2 - Coupling of the palladium-bis(isocyanide) complexes cis-[PdCl2(CNR)2] (R = 2,6-Me2C6H3 1, 2-Cl-6-MeC6H3 2) with benzene-1,3-diamine (BDA1) leads to the diaminocarbene species cis-[PdCl2(CNR){C(NHR)=NH(1,3-C6H4NH2)}] (5 and 6, respectively). In this reaction, BDA1 behaves as a monofunctional nucleophile that adds to one of the RNC ligands by one amino group. By contrast, the reaction of 1 and 2 with benzene-1,4-diamine (BDA2) involves both amino functionalities of the diamine and leads to the binuclear species [cis-PdCl2(CNR){ΜC(NHR)=NH(1,4-C6H4)NH=C(NHR)}-(cis)-PdCl2(CNR)] (6 and 7) featuring two 1,4-bifunctional diaminocarbene ligands. The reaction of cis-[PdCl2(CNR)2] (R = cyclohexyl 3) with either BDA1 or BDA2 does not afford any isolable carbene derivatives. The most versatile chemistry was observed when 1-3 were treated with benzene-1,2-diamine (BDA3) and the relevant substituted 1,2-diamines, viz., 4,5-dimethylbenzene-1,2-diamine (BDA4) and 4,5-dichlorobenzene-1,2-diamine (BDA5). The addition of these diamines brings about the formation of the monocarbene cationic complexes cis-[PdCl(CNR){C(NHR)=NHC6H2X2NH2}]Cl (X = H, Me, Cl) (8-16), the Chugaev-type C,C-bound bis-carbenes cis-[PdCl2{C(NHR)=NHC6H2X2NH=C(NHR)}] (17, 18), and the bis(C,N-chelated)carbene complexes cis-[Pd{C(NHR)=NHC6H2X2NH2}2]Cl2 (19-24). All prepared complexes (with the exception of 17 and 18) were isolated as colorless or pale yellow solids and characterized by elemental analyses (C, H, N), HRESI±-MS, IR, 1H and 13C{1H} NMR spectroscopies, and 4, 7, 13, 16, and 24 by X-ray diffraction. Complexes 17 and 18 were characterized by HRESI±-MS and IR spectroscopy, and their structures were established by X-ray crystallography.

AB - Coupling of the palladium-bis(isocyanide) complexes cis-[PdCl2(CNR)2] (R = 2,6-Me2C6H3 1, 2-Cl-6-MeC6H3 2) with benzene-1,3-diamine (BDA1) leads to the diaminocarbene species cis-[PdCl2(CNR){C(NHR)=NH(1,3-C6H4NH2)}] (5 and 6, respectively). In this reaction, BDA1 behaves as a monofunctional nucleophile that adds to one of the RNC ligands by one amino group. By contrast, the reaction of 1 and 2 with benzene-1,4-diamine (BDA2) involves both amino functionalities of the diamine and leads to the binuclear species [cis-PdCl2(CNR){ΜC(NHR)=NH(1,4-C6H4)NH=C(NHR)}-(cis)-PdCl2(CNR)] (6 and 7) featuring two 1,4-bifunctional diaminocarbene ligands. The reaction of cis-[PdCl2(CNR)2] (R = cyclohexyl 3) with either BDA1 or BDA2 does not afford any isolable carbene derivatives. The most versatile chemistry was observed when 1-3 were treated with benzene-1,2-diamine (BDA3) and the relevant substituted 1,2-diamines, viz., 4,5-dimethylbenzene-1,2-diamine (BDA4) and 4,5-dichlorobenzene-1,2-diamine (BDA5). The addition of these diamines brings about the formation of the monocarbene cationic complexes cis-[PdCl(CNR){C(NHR)=NHC6H2X2NH2}]Cl (X = H, Me, Cl) (8-16), the Chugaev-type C,C-bound bis-carbenes cis-[PdCl2{C(NHR)=NHC6H2X2NH=C(NHR)}] (17, 18), and the bis(C,N-chelated)carbene complexes cis-[Pd{C(NHR)=NHC6H2X2NH2}2]Cl2 (19-24). All prepared complexes (with the exception of 17 and 18) were isolated as colorless or pale yellow solids and characterized by elemental analyses (C, H, N), HRESI±-MS, IR, 1H and 13C{1H} NMR spectroscopies, and 4, 7, 13, 16, and 24 by X-ray diffraction. Complexes 17 and 18 were characterized by HRESI±-MS and IR spectroscopy, and their structures were established by X-ray crystallography.

UR - http://www.scopus.com/inward/record.url?scp=84955580023&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.5b00936

DO - 10.1021/acs.organomet.5b00936

M3 - Article

VL - 35

SP - 218

EP - 228

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 2

ER -

ID: 7552424