Facile Ni(II)/ketoxime-mediated conversion of organonitriles into imidoylamidine ligands. Synthesis of imidoylamidines and acetyl amides

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Facile Ni(II)/ketoxime-mediated conversion of organonitriles into imidoylamidine ligands. Synthesis of imidoylamidines and acetyl amides

Kopylovich, M. N. (author)

Pombeiro, A. J. L. (author)

Fischer, Andreas (author): KTH,Kemi

Kloo, Lars A. (author): KTH,Kemi

Kukushkin, V. Y. (author)

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(creator_code:org_t)

2003-10-02
2003
English.
In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 42:22, s. 7239-7248

Related links:: https://urn.kb.se/re...; show more...; https://doi.org/10.1...; show less...

Journal article (peer-reviewed)

Abstract Subject headings

Treatment of alkyl nitriles with NiX2.6H(2)O (X = Cl, NO3) and 2-propanone oxime, followed by (X = Cl) addition of [i-Pr4N](NO3) for precipitation of the product, resulted in the formation of amidinium nitrates [RC(=NH2)NH2](NO3) (R = Me, Et, n-Pr), The reaction went to another direction with NiX2.2H(2)O, i.e., the reaction between neat RCN (R = Me, Et, n-Pr, i-Pr, n-Bu, CH2Cl, CH2C6H4OMe-p) and NiCl2.2H(2)O/2-propanone oxime (other ketoximes can also be used) gave the (imidoylamidine)Ni(II) complexes [Ni{(N) under bar (H)=C(R)NHC(R)=(N) under barH}(2)](2+) (1(2+)-7(2+)). The latter were isolated in good yields (65-91%) as the bis-chloride salts 1.Cl-2-6.Cl-2 and the mixed salt 7.(Cl)(p-MeOC6H4CH2CO2). Remarkably, the latter transformation does not proceed at all if NiCl2.2H(2)O or the ketoxime are taken alone. Liberation of imidoylamidines was performed for one alkyl-containing complex [2.Cl-2] and one benzyl-containing complex [7.(Cl)(p-MeOC6H4CH2CO2)], by (i) addition of HBF4.Et2O to the acetonitrile solution of the complexes to yield [N(H)=C(R)NHC(R)=NH].2HBF(4) (R = Et 8 and R = CH2C6H4OMe-p 9) or (ii) substitution for ethanediamine (en) with following precipitation of the complex [Ni(en)(3)]Cl-2 with formation of free N(H) C(R)NHC(R)=NH (R = Et 10 and R = CH2C6H4OMe-p 11). In contrast to the liberation in nonaqueous media, treatment of 2.Cl-2 and 7.(CI)(P-MeOC6H4CH2CO2) with Na(2)EDTA.2H(2)O in water-methanol solutions led to substitution and hydrolysis to furnish the acyl amides {EtC(=O)} 2NH (12) and {p-MeOC6H4CH2C(=0)}(2)NH (13). Alternatively, 12 and 13 were obtained by hydrolysis of 10 and 11 in water at pH ca. 8.5. It was shown that the oxime complexes trans-[NiCl2(C4H8C=NOH)(4)] (14) or cis-[Ni(O,O-NO3)(2)(C4H8C=NOH)(2)] (15) can be intermediates in the formation of amidines and imidoylamidines. The sequence of the Ni(II)/oxime mediated formation of (imidoylamidine)Ni complexes and liberation (or hydrolytic liberation) of the ligands opens up a novel, facile and environmentally benign route to imidoylamidines and acyl amides.

Keyword

metal-mediated hydrolysis
phospha-s-triazines
coordinated nitriles
nickel(ii) site
nitro-compounds
samarium(ii) iodide
crystal-structure
acyclic imides
complexes
amidines

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By the author/editor: Kopylovich, M. N ...; Pombeiro, A. J. ...; Fischer, Andreas; Kloo, Lars A.; Kukushkin, V. Y.

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By the university: Royal Institute of Technology

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