An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes
Treatment of the double nuclear complex <b>1a</b>, di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh (triphos) and NH<sub>4</sub>PF<sub...
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MDPI AG
2023-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/5/2328 |
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| author | Basma al Janabi Francisco Reigosa Gemma Alberdi Juan M. Ortigueira José M. Vila |
| author_facet | Basma al Janabi Francisco Reigosa Gemma Alberdi Juan M. Ortigueira José M. Vila |
| author_sort | Basma al Janabi |
| collection | DOAJ |
| description | Treatment of the double nuclear complex <b>1a</b>, di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh (triphos) and NH<sub>4</sub>PF<sub>6</sub> gave the single nuclear species <b>2a</b>, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of <b>2a</b> with Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>NH<sub>2</sub> in refluxing chloroform via a condensation reaction of the amine and formyl groups to produce the C=N double bond, gave <b>3a</b>, 1-N-(cyclohexylamine)-4- N-(diphenylphosphinoethylamine)palladium(triphos)(hexafluorophasphate); a potentially bidentate [<i>N</i>,<i>P</i>] metaloligand. However, attempts to coordinate a second metal by treatment of 3a with [PdCl<sub>2</sub>(PhCN)<sub>2</sub>] were to no avail. Notwithstanding, complexes <b>2a</b> and <b>3a</b> left to stand in solution spontaneously self-transformed to give in either case the double nuclear complex <b>10</b>, 1,4-N,N-terephthalylidene(cyclohexilamine)-3,6-[bispalladium(triphos)]di(hexafluorophosphate), after undergoing further metalation of the phenyl ring, then bearing two mutually <i>trans</i> [Pd(Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh)-<i>P</i>,<i>P</i>,<i>P</i>] 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<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh (triphos) and NH<sub>4</sub>PF<sub>6</sub> gave the single nuclear species <b>2b</b>, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate), Treatment of <b>2b</b> with H<sub>2</sub>O/glacial MeCOOH gave cleavage of the C=N double bond and of the Pd···N interaction, yielding <b>5b</b>, isophthalaldehyde-6-palladium(triphos)hexafluorophosphate, which then reacted with Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>3</sub>NH<sub>2</sub> to yield complex <b>6b</b>, N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)di(hexafluorophosphate), with two pairs of non-coordinated nitrogen and phosphorus donor atoms. Treatment of <b>6b</b> with [PdCl<sub>2</sub>(PhCN)<sub>2</sub>], [PtCl<sub>2</sub>(PhCN)<sub>2</sub>], or [PtMe<sub>2</sub>(COD)] gave the new double nuclear complexes <b>7b</b>, <b>8b</b> and <b>9b</b>, palladiumdichloro-, platinumdichloro- and platinumdimethyl[N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)(hexafluorophosphate)-P,P], respectively, showing the behavior of <b>6b</b> as a palladated bidentate [<i>P</i>,<i>P</i>] metaloligand. The complexes were fully characterized by microanalysis, IR, <sup>1</sup>H, and <sup>31</sup>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. |
| first_indexed | 2024-03-11T07:17:03Z |
| format | Article |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T07:17:03Z |
| publishDate | 2023-03-01 |
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| series | Molecules |
| spelling | doaj.art-d3792f58feb64d43898fa3ec33cf68ea2023-11-17T08:15:09ZengMDPI AGMolecules1420-30492023-03-01285232810.3390/molecules28052328An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated ComplexesBasma al Janabi0Francisco Reigosa1Gemma Alberdi2Juan M. Ortigueira3José M. Vila4Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, SpainDepartment of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, SpainDepartment of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, SpainDepartment of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, SpainDepartment of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, SpainTreatment of the double nuclear complex <b>1a</b>, di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh (triphos) and NH<sub>4</sub>PF<sub>6</sub> gave the single nuclear species <b>2a</b>, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of <b>2a</b> with Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>NH<sub>2</sub> in refluxing chloroform via a condensation reaction of the amine and formyl groups to produce the C=N double bond, gave <b>3a</b>, 1-N-(cyclohexylamine)-4- N-(diphenylphosphinoethylamine)palladium(triphos)(hexafluorophasphate); a potentially bidentate [<i>N</i>,<i>P</i>] metaloligand. However, attempts to coordinate a second metal by treatment of 3a with [PdCl<sub>2</sub>(PhCN)<sub>2</sub>] were to no avail. Notwithstanding, complexes <b>2a</b> and <b>3a</b> left to stand in solution spontaneously self-transformed to give in either case the double nuclear complex <b>10</b>, 1,4-N,N-terephthalylidene(cyclohexilamine)-3,6-[bispalladium(triphos)]di(hexafluorophosphate), after undergoing further metalation of the phenyl ring, then bearing two mutually <i>trans</i> [Pd(Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh)-<i>P</i>,<i>P</i>,<i>P</i>] 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<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>PPh (triphos) and NH<sub>4</sub>PF<sub>6</sub> gave the single nuclear species <b>2b</b>, 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate), Treatment of <b>2b</b> with H<sub>2</sub>O/glacial MeCOOH gave cleavage of the C=N double bond and of the Pd···N interaction, yielding <b>5b</b>, isophthalaldehyde-6-palladium(triphos)hexafluorophosphate, which then reacted with Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>3</sub>NH<sub>2</sub> to yield complex <b>6b</b>, N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)di(hexafluorophosphate), with two pairs of non-coordinated nitrogen and phosphorus donor atoms. Treatment of <b>6b</b> with [PdCl<sub>2</sub>(PhCN)<sub>2</sub>], [PtCl<sub>2</sub>(PhCN)<sub>2</sub>], or [PtMe<sub>2</sub>(COD)] gave the new double nuclear complexes <b>7b</b>, <b>8b</b> and <b>9b</b>, palladiumdichloro-, platinumdichloro- and platinumdimethyl[N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)(hexafluorophosphate)-P,P], respectively, showing the behavior of <b>6b</b> as a palladated bidentate [<i>P</i>,<i>P</i>] metaloligand. The complexes were fully characterized by microanalysis, IR, <sup>1</sup>H, and <sup>31</sup>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.https://www.mdpi.com/1420-3049/28/5/2328palladacyclesiminescatalysisSuzukicross coupling |
| spellingShingle | Basma al Janabi Francisco Reigosa Gemma Alberdi Juan M. Ortigueira José M. Vila An Innovative Structural Rearrangement in Imine Palladacycle Metaloligand Chemistry: From Single-Nuclear to Double-Nuclear Pseudo-Pentacoordinated Complexes Molecules palladacycles imines catalysis Suzuki cross coupling |
| 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 | palladacycles imines catalysis Suzuki cross coupling |
| url | https://www.mdpi.com/1420-3049/28/5/2328 |
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