Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

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Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide. / Andrusenko, Elena V.; Kabin, Evgeniy V.; Novikov, Alexander S.; Bokach, Nadezhda A.; Starova, Galina L.; Zolotarev, Andrey A.; Kukushkin, Vadim Yu.

In: European Journal of Inorganic Chemistry, No. 29, 2015, p. 4894-4904.

Research output: Contribution to journal › Article

BibTeX

@article{61d2dd1ddcd84f19af7d374e93691f44,

title = "Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide",

abstract = "Nickel(II)-mediated coupling between the cyanamide Me2NCN and the ketoximes Me(R)C=NOH (R = Me, Ph) gives chelates of the general formula [NiClx(H2O)(y){HN=C(NMe2)(ON=C(R)Me)}(2)](n+) ([1](+): R = Me; x = 1, y = 0; salts with both Cl- and [NiCl4](2-) were isolated; [2](2+): R = Me; x = 0, y = 2; salt with Cl- was isolated; [3](+): R = Ph; x = 1, y = 1; salt with Cl- was isolated) and the iminium salts [H2N=C(NMe2)ON=C(R)Me](+) ([4](+): R = Me; salt with [NiCl4](2-) was isolated; [5](+): R = Ph; salt with Cl- was isolated). This reaction demonstrates the difference in the reactivity between conventional nitriles and dialkylcyanamides: whereas nitriles RCN (R = Alk, Ar) react with Ni-II/ketoxime systems to afford (1,3,5-triazapentadiene)Ni-II species, formed by postulated nitrile-oxime coupling intermediates, cyanamides under the same conditions give either stable cyanamide-oxime coupling products or the Busch-type complex [Ni{HN=C(Me)CH2C(Me-2)NH2}(2)]Cl-2 ([6]Cl-2). The reason for the different stability of t",

author = "Andrusenko, {Elena V.} and Kabin, {Evgeniy V.} and Novikov, {Alexander S.} and Bokach, {Nadezhda A.} and Starova, {Galina L.} and Zolotarev, {Andrey A.} and Kukushkin, {Vadim Yu.}",

year = "2015",

doi = "10.1002/ejic.201500693",

language = "English",

pages = "4894--4904",

journal = "Berichte der deutschen chemischen Gesellschaft",

issn = "0365-9496",

publisher = "Wiley-Blackwell",

number = "29",

}

RIS

TY - JOUR

T1 - Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

AU - Andrusenko, Elena V.

AU - Kabin, Evgeniy V.

AU - Novikov, Alexander S.

AU - Bokach, Nadezhda A.

AU - Starova, Galina L.

AU - Zolotarev, Andrey A.

AU - Kukushkin, Vadim Yu.

PY - 2015

Y1 - 2015

N2 - Nickel(II)-mediated coupling between the cyanamide Me2NCN and the ketoximes Me(R)C=NOH (R = Me, Ph) gives chelates of the general formula [NiClx(H2O)(y){HN=C(NMe2)(ON=C(R)Me)}(2)](n+) ([1](+): R = Me; x = 1, y = 0; salts with both Cl- and [NiCl4](2-) were isolated; [2](2+): R = Me; x = 0, y = 2; salt with Cl- was isolated; [3](+): R = Ph; x = 1, y = 1; salt with Cl- was isolated) and the iminium salts [H2N=C(NMe2)ON=C(R)Me](+) ([4](+): R = Me; salt with [NiCl4](2-) was isolated; [5](+): R = Ph; salt with Cl- was isolated). This reaction demonstrates the difference in the reactivity between conventional nitriles and dialkylcyanamides: whereas nitriles RCN (R = Alk, Ar) react with Ni-II/ketoxime systems to afford (1,3,5-triazapentadiene)Ni-II species, formed by postulated nitrile-oxime coupling intermediates, cyanamides under the same conditions give either stable cyanamide-oxime coupling products or the Busch-type complex [Ni{HN=C(Me)CH2C(Me-2)NH2}(2)]Cl-2 ([6]Cl-2). The reason for the different stability of t

AB - Nickel(II)-mediated coupling between the cyanamide Me2NCN and the ketoximes Me(R)C=NOH (R = Me, Ph) gives chelates of the general formula [NiClx(H2O)(y){HN=C(NMe2)(ON=C(R)Me)}(2)](n+) ([1](+): R = Me; x = 1, y = 0; salts with both Cl- and [NiCl4](2-) were isolated; [2](2+): R = Me; x = 0, y = 2; salt with Cl- was isolated; [3](+): R = Ph; x = 1, y = 1; salt with Cl- was isolated) and the iminium salts [H2N=C(NMe2)ON=C(R)Me](+) ([4](+): R = Me; salt with [NiCl4](2-) was isolated; [5](+): R = Ph; salt with Cl- was isolated). This reaction demonstrates the difference in the reactivity between conventional nitriles and dialkylcyanamides: whereas nitriles RCN (R = Alk, Ar) react with Ni-II/ketoxime systems to afford (1,3,5-triazapentadiene)Ni-II species, formed by postulated nitrile-oxime coupling intermediates, cyanamides under the same conditions give either stable cyanamide-oxime coupling products or the Busch-type complex [Ni{HN=C(Me)CH2C(Me-2)NH2}(2)]Cl-2 ([6]Cl-2). The reason for the different stability of t

U2 - 10.1002/ejic.201500693

DO - 10.1002/ejic.201500693

M3 - Article

SP - 4894

EP - 4904

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 29

ER -

ID: 4000204