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An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes

Treatment of the double nuclear complex 1a, di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph(2)PCH(2)CH(2))(2)PPh (triphos) and NH(4)PF(6) gave the single nuclear species 2a, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of 2a w...

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Autores principales: al Janabi, Basma, Reigosa, Francisco, Alberdi, Gemma, Ortigueira, Juan M., Vila, José M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10005383/
https://www.ncbi.nlm.nih.gov/pubmed/36903573
http://dx.doi.org/10.3390/molecules28052328
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author al Janabi, Basma
Reigosa, Francisco
Alberdi, Gemma
Ortigueira, Juan M.
Vila, José M.
author_facet al Janabi, Basma
Reigosa, Francisco
Alberdi, Gemma
Ortigueira, Juan M.
Vila, José M.
author_sort al Janabi, Basma
collection PubMed
description Treatment of the double nuclear complex 1a, di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph(2)PCH(2)CH(2))(2)PPh (triphos) and NH(4)PF(6) gave the single nuclear species 2a, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of 2a with Ph(2)PCH(2)CH(2)NH(2) in refluxing chloroform via a condensation reaction of the amine and formyl groups to produce the C=N double bond, gave 3a, 1-N-(cyclohexylamine)-4- N-(diphenylphosphinoethylamine)palladium(triphos)(hexafluorophasphate); a potentially bidentate [N,P] metaloligand. However, attempts to coordinate a second metal by treatment of 3a with [PdCl(2)(PhCN)(2)] were to no avail. Notwithstanding, complexes 2a and 3a left to stand in solution spontaneously self-transformed to give in either case the double nuclear complex 10, 1,4-N,N-terephthalylidene(cyclohexilamine)-3,6-[bispalladium(triphos)]di(hexafluorophosphate), after undergoing further metalation of the phenyl ring, then bearing two mutually trans [Pd(Ph(2)PCH(2)CH(2))(2)PPh)-P,P,P] moieties: an unprecedented and serendipitous result indeed. On the other hand, reaction of the double nuclear complex 1b, di-μ-cloro-bis[N-(3-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph(2)PCH(2)CH(2))(2)PPh (triphos) and NH(4)PF(6) gave the single nuclear species 2b, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate), Treatment of 2b with H(2)O/glacial MeCOOH gave cleavage of the C=N double bond and of the Pd···N interaction, yielding 5b, isophthalaldehyde-6-palladium(triphos)hexafluorophosphate, which then reacted with Ph(2)P(CH(2))(3)NH(2) to yield complex 6b, N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)di(hexafluorophosphate), with two pairs of non-coordinated nitrogen and phosphorus donor atoms. Treatment of 6b with [PdCl(2)(PhCN)(2)], [PtCl(2)(PhCN)(2)], or [PtMe(2)(COD)] gave the new double nuclear complexes 7b, 8b and 9b, palladiumdichloro-, platinumdichloro- and platinumdimethyl[N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)(hexafluorophosphate)-P,P], respectively, showing the behavior of 6b as a palladated bidentate [P,P] metaloligand. The complexes were fully characterized by microanalysis, IR, (1)H, and (31)P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 10 and 5b have been previously described as the perchlorate salts by JM Vila et al.
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spelling pubmed-100053832023-03-11 An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes al Janabi, Basma Reigosa, Francisco Alberdi, Gemma Ortigueira, Juan M. Vila, José M. Molecules Article Treatment of the double nuclear complex 1a, di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph(2)PCH(2)CH(2))(2)PPh (triphos) and NH(4)PF(6) gave the single nuclear species 2a, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of 2a with Ph(2)PCH(2)CH(2)NH(2) in refluxing chloroform via a condensation reaction of the amine and formyl groups to produce the C=N double bond, gave 3a, 1-N-(cyclohexylamine)-4- N-(diphenylphosphinoethylamine)palladium(triphos)(hexafluorophasphate); a potentially bidentate [N,P] metaloligand. However, attempts to coordinate a second metal by treatment of 3a with [PdCl(2)(PhCN)(2)] were to no avail. Notwithstanding, complexes 2a and 3a left to stand in solution spontaneously self-transformed to give in either case the double nuclear complex 10, 1,4-N,N-terephthalylidene(cyclohexilamine)-3,6-[bispalladium(triphos)]di(hexafluorophosphate), after undergoing further metalation of the phenyl ring, then bearing two mutually trans [Pd(Ph(2)PCH(2)CH(2))(2)PPh)-P,P,P] moieties: an unprecedented and serendipitous result indeed. On the other hand, reaction of the double nuclear complex 1b, di-μ-cloro-bis[N-(3-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph(2)PCH(2)CH(2))(2)PPh (triphos) and NH(4)PF(6) gave the single nuclear species 2b, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate), Treatment of 2b with H(2)O/glacial MeCOOH gave cleavage of the C=N double bond and of the Pd···N interaction, yielding 5b, isophthalaldehyde-6-palladium(triphos)hexafluorophosphate, which then reacted with Ph(2)P(CH(2))(3)NH(2) to yield complex 6b, N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)di(hexafluorophosphate), with two pairs of non-coordinated nitrogen and phosphorus donor atoms. Treatment of 6b with [PdCl(2)(PhCN)(2)], [PtCl(2)(PhCN)(2)], or [PtMe(2)(COD)] gave the new double nuclear complexes 7b, 8b and 9b, palladiumdichloro-, platinumdichloro- and platinumdimethyl[N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)(hexafluorophosphate)-P,P], respectively, showing the behavior of 6b as a palladated bidentate [P,P] metaloligand. The complexes were fully characterized by microanalysis, IR, (1)H, and (31)P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 10 and 5b have been previously described as the perchlorate salts by JM Vila et al. MDPI 2023-03-02 /pmc/articles/PMC10005383/ /pubmed/36903573 http://dx.doi.org/10.3390/molecules28052328 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
al Janabi, Basma
Reigosa, Francisco
Alberdi, Gemma
Ortigueira, Juan M.
Vila, José M.
An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
title An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
title_full An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
title_fullStr An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
title_full_unstemmed An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
title_short An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
title_sort innovative structural rearrangement in imine palladacycle metaloligand chemistry: from single-nuclear to double-nuclear pseudo-pentacoordinated complexes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10005383/
https://www.ncbi.nlm.nih.gov/pubmed/36903573
http://dx.doi.org/10.3390/molecules28052328
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