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Facile Ni(II)/Ketoxime-Mediated Conversion of Organonitriles into Imidoylamidine Ligands. Synthesis of Imidoylamidines and Acetyl Amides

Treatment of alkyl nitriles with NiX2·6H2O (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 NiX2·2H2...

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Published in:Inorganic chemistry 2003-11, Vol.42 (22), p.7239-7248
Main Authors: Kopylovich, Maximilian N, Pombeiro, Armando J. L, Fischer, Andreas, Kloo, Lars, Kukushkin, Vadim Yu
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cited_by cdi_FETCH-LOGICAL-a386t-9073fb09db6b46fcbb36441aeb500078ab822f44281fda4de4321573a2a420413
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description Treatment of alkyl nitriles with NiX2·6H2O (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 NiX2·2H2O, i.e., the reaction between neat RCN (R = Me, Et, n-Pr, i-Pr, n-Bu, CH2Cl, CH2C6H4OMe-p) and NiCl2·2H2O/2-propanone oxime (other ketoximes can also be used) gave the (imidoylamidine)Ni(II) complexes [Ni{N(H)C(R)NHC(R)NH}2]2+ (1 2+−7 2+). The latter were isolated in good yields (65−91%) as the bis-chloride salts 1·Cl2−6·Cl2 and the mixed salt 7·(Cl)(p-MeOC6H4CH2CO2). Remarkably, the latter transformation does not proceed at all if NiCl2·2H2O or the ketoxime are taken alone. Liberation of imidoylamidines was performed for one alkyl-containing complex [2·Cl2] 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]·2HBF4 (R = Et 8 and R = CH2C6H4OMe-p 9) or (ii) substitution for ethanediamine (en) with following precipitation of the complex [Ni(en)3]Cl2 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·Cl2 and 7·(Cl)(p-MeOC6H4CH2CO2) with Na2EDTA·2H2O in water−methanol solutions led to substitution and hydrolysis to furnish the acyl amides {EtC(O)}2NH (12) and {p-MeOC6H4CH2C(O)}2NH (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.
doi_str_mv 10.1021/ic0349813
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Synthesis of Imidoylamidines and Acetyl Amides</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Kopylovich, Maximilian N ; Pombeiro, Armando J. L ; Fischer, Andreas ; Kloo, Lars ; Kukushkin, Vadim Yu</creator><creatorcontrib>Kopylovich, Maximilian N ; Pombeiro, Armando J. L ; Fischer, Andreas ; Kloo, Lars ; Kukushkin, Vadim Yu</creatorcontrib><description>Treatment of alkyl nitriles with NiX2·6H2O (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 NiX2·2H2O, i.e., the reaction between neat RCN (R = Me, Et, n-Pr, i-Pr, n-Bu, CH2Cl, CH2C6H4OMe-p) and NiCl2·2H2O/2-propanone oxime (other ketoximes can also be used) gave the (imidoylamidine)Ni(II) complexes [Ni{N(H)C(R)NHC(R)NH}2]2+ (1 2+−7 2+). The latter were isolated in good yields (65−91%) as the bis-chloride salts 1·Cl2−6·Cl2 and the mixed salt 7·(Cl)(p-MeOC6H4CH2CO2). Remarkably, the latter transformation does not proceed at all if NiCl2·2H2O or the ketoxime are taken alone. Liberation of imidoylamidines was performed for one alkyl-containing complex [2·Cl2] 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]·2HBF4 (R = Et 8 and R = CH2C6H4OMe-p 9) or (ii) substitution for ethanediamine (en) with following precipitation of the complex [Ni(en)3]Cl2 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·Cl2 and 7·(Cl)(p-MeOC6H4CH2CO2) with Na2EDTA·2H2O in water−methanol solutions led to substitution and hydrolysis to furnish the acyl amides {EtC(O)}2NH (12) and {p-MeOC6H4CH2C(O)}2NH (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.</description><identifier>ISSN: 0020-1669</identifier><identifier>ISSN: 1520-510X</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic0349813</identifier><identifier>PMID: 14577793</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>acyclic imides ; amidines ; complexes ; coordinated nitriles ; crystal-structure ; metal-mediated hydrolysis ; nickel(ii) site ; nitro-compounds ; phospha-s-triazines ; samarium(ii) iodide</subject><ispartof>Inorganic chemistry, 2003-11, Vol.42 (22), p.7239-7248</ispartof><rights>Copyright © 2003 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a386t-9073fb09db6b46fcbb36441aeb500078ab822f44281fda4de4321573a2a420413</citedby><cites>FETCH-LOGICAL-a386t-9073fb09db6b46fcbb36441aeb500078ab822f44281fda4de4321573a2a420413</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/14577793$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-22926$$DView record from Swedish Publication Index$$Hfree_for_read</backlink></links><search><creatorcontrib>Kopylovich, Maximilian N</creatorcontrib><creatorcontrib>Pombeiro, Armando J. L</creatorcontrib><creatorcontrib>Fischer, Andreas</creatorcontrib><creatorcontrib>Kloo, Lars</creatorcontrib><creatorcontrib>Kukushkin, Vadim Yu</creatorcontrib><title>Facile Ni(II)/Ketoxime-Mediated Conversion of Organonitriles into Imidoylamidine Ligands. Synthesis of Imidoylamidines and Acetyl Amides</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>Treatment of alkyl nitriles with NiX2·6H2O (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 NiX2·2H2O, i.e., the reaction between neat RCN (R = Me, Et, n-Pr, i-Pr, n-Bu, CH2Cl, CH2C6H4OMe-p) and NiCl2·2H2O/2-propanone oxime (other ketoximes can also be used) gave the (imidoylamidine)Ni(II) complexes [Ni{N(H)C(R)NHC(R)NH}2]2+ (1 2+−7 2+). The latter were isolated in good yields (65−91%) as the bis-chloride salts 1·Cl2−6·Cl2 and the mixed salt 7·(Cl)(p-MeOC6H4CH2CO2). Remarkably, the latter transformation does not proceed at all if NiCl2·2H2O or the ketoxime are taken alone. Liberation of imidoylamidines was performed for one alkyl-containing complex [2·Cl2] 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]·2HBF4 (R = Et 8 and R = CH2C6H4OMe-p 9) or (ii) substitution for ethanediamine (en) with following precipitation of the complex [Ni(en)3]Cl2 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·Cl2 and 7·(Cl)(p-MeOC6H4CH2CO2) with Na2EDTA·2H2O in water−methanol solutions led to substitution and hydrolysis to furnish the acyl amides {EtC(O)}2NH (12) and {p-MeOC6H4CH2C(O)}2NH (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.</description><subject>acyclic imides</subject><subject>amidines</subject><subject>complexes</subject><subject>coordinated nitriles</subject><subject>crystal-structure</subject><subject>metal-mediated hydrolysis</subject><subject>nickel(ii) site</subject><subject>nitro-compounds</subject><subject>phospha-s-triazines</subject><subject>samarium(ii) iodide</subject><issn>0020-1669</issn><issn>1520-510X</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNpt0d1O2zAUB3Br2jQ62MVeYPLNpiEt4K_EyWVV6KjoAA32cWc5yQkYkrizHUbfYI89o1SdkLg6lv07x7L_CL2j5IASRg9NRbgocspfoAlNGUlSSn69RBNC4ppmWbGD3nh_SwgpuMheox0qUillwSfo71xXpgV8Zj4tFvuHpxDsg-kg-Qq10QFqPLP9PThvbI9tg8_dte5tb4KLTR6bPli86Ext162OxfSAlyaS2h_gy3UfbsAb_9j4FHkcCZ5WENYtnsY98HvoVaNbD283dRd9nx9fzU6S5fmXxWy6TDTPs5AURPKmJEVdZqXImqoseSYE1VCm8Xky12XOWCMEy2lTa1GD4IymkmumBSOC8l30eZzr_8BqKNXKmU67tbLaqCPzY6qsu1Z34UYxVrAs8o8jXzn7ewAfVGd8BW2re7CDV5JykhacRLg_wspZ7x0028mUqMeU1DalaN9vhg5lB_V_uYklgmQExgd42J5rd6cyyWWqri4u1fz06OTbT75UZ9F_GL2uvLq1g-vjFz5z8T-qUaje</recordid><startdate>20031103</startdate><enddate>20031103</enddate><creator>Kopylovich, Maximilian N</creator><creator>Pombeiro, Armando J. 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L ; Fischer, Andreas ; Kloo, Lars ; Kukushkin, Vadim Yu</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a386t-9073fb09db6b46fcbb36441aeb500078ab822f44281fda4de4321573a2a420413</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><topic>acyclic imides</topic><topic>amidines</topic><topic>complexes</topic><topic>coordinated nitriles</topic><topic>crystal-structure</topic><topic>metal-mediated hydrolysis</topic><topic>nickel(ii) site</topic><topic>nitro-compounds</topic><topic>phospha-s-triazines</topic><topic>samarium(ii) iodide</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kopylovich, Maximilian N</creatorcontrib><creatorcontrib>Pombeiro, Armando J. L</creatorcontrib><creatorcontrib>Fischer, Andreas</creatorcontrib><creatorcontrib>Kloo, Lars</creatorcontrib><creatorcontrib>Kukushkin, Vadim Yu</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>SwePub</collection><collection>SwePub Articles</collection><collection>SWEPUB Kungliga Tekniska Högskolan</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kopylovich, Maximilian N</au><au>Pombeiro, Armando J. L</au><au>Fischer, Andreas</au><au>Kloo, Lars</au><au>Kukushkin, Vadim Yu</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Facile Ni(II)/Ketoxime-Mediated Conversion of Organonitriles into Imidoylamidine Ligands. Synthesis of Imidoylamidines and Acetyl Amides</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2003-11-03</date><risdate>2003</risdate><volume>42</volume><issue>22</issue><spage>7239</spage><epage>7248</epage><pages>7239-7248</pages><issn>0020-1669</issn><issn>1520-510X</issn><eissn>1520-510X</eissn><abstract>Treatment of alkyl nitriles with NiX2·6H2O (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 NiX2·2H2O, i.e., the reaction between neat RCN (R = Me, Et, n-Pr, i-Pr, n-Bu, CH2Cl, CH2C6H4OMe-p) and NiCl2·2H2O/2-propanone oxime (other ketoximes can also be used) gave the (imidoylamidine)Ni(II) complexes [Ni{N(H)C(R)NHC(R)NH}2]2+ (1 2+−7 2+). The latter were isolated in good yields (65−91%) as the bis-chloride salts 1·Cl2−6·Cl2 and the mixed salt 7·(Cl)(p-MeOC6H4CH2CO2). Remarkably, the latter transformation does not proceed at all if NiCl2·2H2O or the ketoxime are taken alone. Liberation of imidoylamidines was performed for one alkyl-containing complex [2·Cl2] 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]·2HBF4 (R = Et 8 and R = CH2C6H4OMe-p 9) or (ii) substitution for ethanediamine (en) with following precipitation of the complex [Ni(en)3]Cl2 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·Cl2 and 7·(Cl)(p-MeOC6H4CH2CO2) with Na2EDTA·2H2O in water−methanol solutions led to substitution and hydrolysis to furnish the acyl amides {EtC(O)}2NH (12) and {p-MeOC6H4CH2C(O)}2NH (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.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>14577793</pmid><doi>10.1021/ic0349813</doi><tpages>10</tpages></addata></record>
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source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects acyclic imides
amidines
complexes
coordinated nitriles
crystal-structure
metal-mediated hydrolysis
nickel(ii) site
nitro-compounds
phospha-s-triazines
samarium(ii) iodide
title Facile Ni(II)/Ketoxime-Mediated Conversion of Organonitriles into Imidoylamidine Ligands. Synthesis of Imidoylamidines and Acetyl Amides
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