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Endohedral Plumbaspherenes of the Group 9 Metals: Synthesis, Structure and Properties of the [M@Pb12]3− (M=Co, Rh, Ir) Ions

dc.contributor.authorLi A.-M.
dc.contributor.authorWang Y.
dc.contributor.authorDowning D.O.
dc.contributor.authorChen F.
dc.contributor.authorZavalij P.
dc.contributor.authorMuñoz-Castro A.
dc.contributor.authorEichhorn B.W.
dc.date.accessioned2020-09-02T22:21:44Z
dc.date.available2020-09-02T22:21:44Z
dc.date.issued2020
dc.identifier10.1002/chem.201905451
dc.identifier.citation26, 26, 5824-5833
dc.identifier.issn09476539
dc.identifier.urihttps://hdl.handle.net/20.500.12728/5076
dc.descriptionThe icosahedral [M@Pb12]3− (M=Co(1), Rh(2), Ir(3)) cluster ions were prepared from K4Pb9 and Co(dppe)Cl2 (dppe=1,2-bis(diphenylphosphino)ethane)/[Rh(PPh3)3Cl]/[Ir(cod)Cl]2 (cod=1,5-cyclooctadiene), respectively, in the presence of 18-crown-6/ 2,2,2-cryptand in ethylenediamine/toluene solvent mixtures. The [K(2,2,2-cryptand)]+ salt of 1 and the [K(18-crown-6)]+ salt of 3 were characterized via X-ray crystallography; the ions 1 and 3 are isostructural and isoelectronic to the [Rh@Pb12]3− (2) ion as well as to the group 10 clusters [M′@Pb12]2− (M′=Ni, Pd, Pt). The ions are all 26-electron clusters with near perfect icosahedral Ih point symmetry. Clusters 1–3 show record downfield 207Pb NMR chemical shifts due to σ-aromaticity of the cluster framework. Calculated and observed 207Pb NMR chemical shifts and 207Pb–xM J-couplings (xM=59Co, 103Rh, 193Ir) are in excellent agreement and DFT analysis shows that the variations of 207Pb NMR chemical shifts for the [M@Pb12]2, 3− ions (M=Co, Rh, Ir, Ni, Pd, Pt) are mainly governed by the perpendicularly oriented σ11 component of the chemical shift anisotropy tensor. The laser desorption ionization time-of-flight (LDI-TOF) mass spectra contain the molecular ions as well as several new gas phase clusters derived from the parents. The DFT-minimized structures of these ions are described. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
dc.language.isoen
dc.publisherWiley-VCH Verlag
dc.subjectcluster compounds
dc.subjecticosahedral
dc.subjectlead
dc.subjectNMR spectroscopy
dc.subjectZintl ion
dc.subjectBinary alloys
dc.subjectChemical analysis
dc.subjectChemical shift
dc.subjectCobalt alloys
dc.subjectCrown ethers
dc.subjectIonization of gases
dc.subjectIons
dc.subjectMass spectrometry
dc.subjectPotassium alloys
dc.subjectX ray crystallography
dc.subject1 ,5-cyclooctadiene
dc.subjectChemical shift anisotropy
dc.subjectCluster framework
dc.subjectGas-phase clusters
dc.subjectLaser desorption ionization
dc.subjectNMR chemical shifts
dc.subjectSigma aromaticity
dc.subjectStructure and properties
dc.subjectLead alloys
dc.titleEndohedral Plumbaspherenes of the Group 9 Metals: Synthesis, Structure and Properties of the [M@Pb12]3− (M=Co, Rh, Ir) Ions
dc.typeArticle


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