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- Kopylovich, M. N. (författare)
Facile Ni(II)/ketoxime-mediated conversion of organonitriles into imidoylamidine ligands. Synthesis of imidoylamidines and acetyl amides
- Artikel/kapitelEngelska2003
Förlag, utgivningsår, omfång ...
- 2003-10-02
- American Chemical Society (ACS),2003
- printrdacarrier
Nummerbeteckningar
- LIBRIS-ID:oai:DiVA.org:kth-22926
- https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-22926URI
- https://doi.org/10.1021/ic0349813DOI
Kompletterande språkuppgifter
- Språk:engelska
- Sammanfattning på:engelska
Ingår i deldatabas
- SwePubSwePub
Klassifikation
Anmärkningar
- QC 20100525
- 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.
Ämnesord och genrebeteckningar
- metal-mediated hydrolysis
- phospha-s-triazines
- coordinated nitriles
- nickel(ii) site
- nitro-compounds
- samarium(ii) iodide
- crystal-structure
- acyclic imides
- complexes
- amidines
Biuppslag (personer, institutioner, konferenser, titlar ...)
- Pombeiro, A. J. L. (författare)
- Fischer, AndreasKTH,Kemi(Swepub:kth)u1mpcad5 (författare)
- Kloo, Lars A.KTH,Kemi(Swepub:kth)u1jrdr1m (författare)
- Kukushkin, V. Y. (författare)
- KTHKemi (creator_code:org_t)
Sammanhörande titlar
- Ingår i:Inorganic Chemistry: American Chemical Society (ACS)42:22, s. 7239-72480020-16691520-510X
Internetlänk
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- Kopylovich, M. N ...
- Pombeiro, A. J. ...
- Fischer, Andreas
- Kloo, Lars A.
- Kukushkin, V. Y.
- Artiklar i publikationen
- Inorganic Chemis ...
- Av lärosätet
- Kungliga Tekniska Högskolan
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