Georgina Rai, Martí Garçon, Philip W. Miller and Mark R. Crimmin*,
{"title":"闪光通讯：金属锌还原二氯化钯前驱体的Pd2Zn2簇","authors":"Georgina Rai, Martí Garçon, Philip W. Miller and Mark R. Crimmin*, ","doi":"10.1021/acs.organomet.4c0050610.1021/acs.organomet.4c00506","DOIUrl":null,"url":null,"abstract":"<p >We report the synthesis and solid-state characterization of two unusual Pd<sub>2</sub>Zn<sub>2</sub> clusters formed from the partial reduction of [PdL<sub>2</sub>Cl<sub>2</sub>] precursors (L<sub>2</sub> = dcpe or dppe) with metallic zinc. The new clusters have been characterized by single crystal X-ray diffraction and contain a Pd<sub>2</sub>Zn<sub>2</sub>Cl<sub>3</sub> core capped by two chelating phosphine ligands with Zn in the formal +1.5 oxidation state. While they possess a near tetrahedral arrangement of metal ions, calculations and bonding analysis (NBO, AIM) suggest that there is limited Zn- - -Zn bonding in these species. Characterization in the solution state is suggestive of dynamic behavior on dissolution, with both diamagnetic and paramagnetic species observed by NMR and EPR spectroscopy. One of these Pd<sub>2</sub>Zn<sub>2</sub> clusters was shown to be an effective precursor for the homocoupling of an aryl bromide.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 6","pages":"716–719 716–719"},"PeriodicalIF":2.5000,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00506","citationCount":"0","resultStr":"{\"title\":\"Flash Communication: Pd2Zn2 Clusters from the Reduction of Palladium(II) Dichloride Precursors with Metallic Zinc\",\"authors\":\"Georgina Rai, Martí Garçon, Philip W. Miller and Mark R. Crimmin*, \",\"doi\":\"10.1021/acs.organomet.4c0050610.1021/acs.organomet.4c00506\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We report the synthesis and solid-state characterization of two unusual Pd<sub>2</sub>Zn<sub>2</sub> clusters formed from the partial reduction of [PdL<sub>2</sub>Cl<sub>2</sub>] precursors (L<sub>2</sub> = dcpe or dppe) with metallic zinc. The new clusters have been characterized by single crystal X-ray diffraction and contain a Pd<sub>2</sub>Zn<sub>2</sub>Cl<sub>3</sub> core capped by two chelating phosphine ligands with Zn in the formal +1.5 oxidation state. While they possess a near tetrahedral arrangement of metal ions, calculations and bonding analysis (NBO, AIM) suggest that there is limited Zn- - -Zn bonding in these species. Characterization in the solution state is suggestive of dynamic behavior on dissolution, with both diamagnetic and paramagnetic species observed by NMR and EPR spectroscopy. One of these Pd<sub>2</sub>Zn<sub>2</sub> clusters was shown to be an effective precursor for the homocoupling of an aryl bromide.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 6\",\"pages\":\"716–719 716–719\"},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2025-03-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00506\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00506\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00506","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Flash Communication: Pd2Zn2 Clusters from the Reduction of Palladium(II) Dichloride Precursors with Metallic Zinc
We report the synthesis and solid-state characterization of two unusual Pd2Zn2 clusters formed from the partial reduction of [PdL2Cl2] precursors (L2 = dcpe or dppe) with metallic zinc. The new clusters have been characterized by single crystal X-ray diffraction and contain a Pd2Zn2Cl3 core capped by two chelating phosphine ligands with Zn in the formal +1.5 oxidation state. While they possess a near tetrahedral arrangement of metal ions, calculations and bonding analysis (NBO, AIM) suggest that there is limited Zn- - -Zn bonding in these species. Characterization in the solution state is suggestive of dynamic behavior on dissolution, with both diamagnetic and paramagnetic species observed by NMR and EPR spectroscopy. One of these Pd2Zn2 clusters was shown to be an effective precursor for the homocoupling of an aryl bromide.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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