Manisha Lakshman , Ghada Al Assi , Rekha MM , Shaker Al-Hasnaawei , Subhashree Ray , Amrita Pal , Renu Sharma
{"title":"MWCNTs/ MNPs-Bis (Py)/ Tu-Pd(0)纳米复合材料催化C-P交叉偶联反应制备三烷基膦的绿色高效途径","authors":"Manisha Lakshman , Ghada Al Assi , Rekha MM , Shaker Al-Hasnaawei , Subhashree Ray , Amrita Pal , Renu Sharma","doi":"10.1016/j.jorganchem.2025.123839","DOIUrl":null,"url":null,"abstract":"<div><div>We report an efficient and sustainable synthesis of triarylphosphines using a novel heterogeneous catalyst: palladium(0) supported on multi-walled carbon nanotubes and magnetic nanoparticles functionalized with bis(pyridyl) thiosemicarbazone ligands (MWCNTs/MNPs–Bis(Py)/Tu–Pd(0)). The catalytic system delivers high activity, achieving up to 94 % isolated yield of triphenylphosphane in a short time (2 h) under mild conditions (80 °C, KOAc, 2-MeTHF). Relative to existing methods, the approach offers faster reactions, higher yields, milder and greener reaction conditions, and enhanced operational simplicity. The use of 2-MeTHF as a green solvent and KOAc as a benign base reinforces the method's environmental credentials. Magnetic nanoparticles enable straightforward magnetic separation and excellent recyclability over multiple cycles with negligible performance loss. The superior activity arises from a combination of high surface area and efficient Pd(0) dispersion, reinforced by strong metal–ligand coordination from the Bis(Py)/Tu ligands on the functionalized MWCNT/MNP support. Comprehensive catalyst characterization—including FT-IR, TEM, VSM, and XRD supports a robust structure–function relationship and a classical Pd(0)/Pd(II) catalytic cycle involving oxidative addition, phosphine coordination, deprotonation where applicable, and reductive elimination to furnish the target triarylphosphine. Demonstrated across twenty substrate examples (72–97 % yields) with eight consecutive reuse cycles and minimal activity decline, this Pd(0) on MWCNTs/MNPs–Bis(Py)/Tu catalyst represents a cost-effective, green, and scalable platform for triphenylphosphane synthesis with broad applicability in organic synthesis and industrial catalysis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1041 ","pages":"Article 123839"},"PeriodicalIF":2.1000,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A green and efficient route to triarylphosphines via C–P cross-coupling reactions catalyzed by MWCNTs/MNPs–Bis(Py)/Tu–Pd(0) nanocomposite\",\"authors\":\"Manisha Lakshman , Ghada Al Assi , Rekha MM , Shaker Al-Hasnaawei , Subhashree Ray , Amrita Pal , Renu Sharma\",\"doi\":\"10.1016/j.jorganchem.2025.123839\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>We report an efficient and sustainable synthesis of triarylphosphines using a novel heterogeneous catalyst: palladium(0) supported on multi-walled carbon nanotubes and magnetic nanoparticles functionalized with bis(pyridyl) thiosemicarbazone ligands (MWCNTs/MNPs–Bis(Py)/Tu–Pd(0)). The catalytic system delivers high activity, achieving up to 94 % isolated yield of triphenylphosphane in a short time (2 h) under mild conditions (80 °C, KOAc, 2-MeTHF). Relative to existing methods, the approach offers faster reactions, higher yields, milder and greener reaction conditions, and enhanced operational simplicity. The use of 2-MeTHF as a green solvent and KOAc as a benign base reinforces the method's environmental credentials. Magnetic nanoparticles enable straightforward magnetic separation and excellent recyclability over multiple cycles with negligible performance loss. The superior activity arises from a combination of high surface area and efficient Pd(0) dispersion, reinforced by strong metal–ligand coordination from the Bis(Py)/Tu ligands on the functionalized MWCNT/MNP support. Comprehensive catalyst characterization—including FT-IR, TEM, VSM, and XRD supports a robust structure–function relationship and a classical Pd(0)/Pd(II) catalytic cycle involving oxidative addition, phosphine coordination, deprotonation where applicable, and reductive elimination to furnish the target triarylphosphine. Demonstrated across twenty substrate examples (72–97 % yields) with eight consecutive reuse cycles and minimal activity decline, this Pd(0) on MWCNTs/MNPs–Bis(Py)/Tu catalyst represents a cost-effective, green, and scalable platform for triphenylphosphane synthesis with broad applicability in organic synthesis and industrial catalysis.</div></div>\",\"PeriodicalId\":374,\"journal\":{\"name\":\"Journal of Organometallic Chemistry\",\"volume\":\"1041 \",\"pages\":\"Article 123839\"},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2025-08-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Organometallic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022328X25003316\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X25003316","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
A green and efficient route to triarylphosphines via C–P cross-coupling reactions catalyzed by MWCNTs/MNPs–Bis(Py)/Tu–Pd(0) nanocomposite
We report an efficient and sustainable synthesis of triarylphosphines using a novel heterogeneous catalyst: palladium(0) supported on multi-walled carbon nanotubes and magnetic nanoparticles functionalized with bis(pyridyl) thiosemicarbazone ligands (MWCNTs/MNPs–Bis(Py)/Tu–Pd(0)). The catalytic system delivers high activity, achieving up to 94 % isolated yield of triphenylphosphane in a short time (2 h) under mild conditions (80 °C, KOAc, 2-MeTHF). Relative to existing methods, the approach offers faster reactions, higher yields, milder and greener reaction conditions, and enhanced operational simplicity. The use of 2-MeTHF as a green solvent and KOAc as a benign base reinforces the method's environmental credentials. Magnetic nanoparticles enable straightforward magnetic separation and excellent recyclability over multiple cycles with negligible performance loss. The superior activity arises from a combination of high surface area and efficient Pd(0) dispersion, reinforced by strong metal–ligand coordination from the Bis(Py)/Tu ligands on the functionalized MWCNT/MNP support. Comprehensive catalyst characterization—including FT-IR, TEM, VSM, and XRD supports a robust structure–function relationship and a classical Pd(0)/Pd(II) catalytic cycle involving oxidative addition, phosphine coordination, deprotonation where applicable, and reductive elimination to furnish the target triarylphosphine. Demonstrated across twenty substrate examples (72–97 % yields) with eight consecutive reuse cycles and minimal activity decline, this Pd(0) on MWCNTs/MNPs–Bis(Py)/Tu catalyst represents a cost-effective, green, and scalable platform for triphenylphosphane synthesis with broad applicability in organic synthesis and industrial catalysis.
期刊介绍:
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.