Elimination of the spectral interference from polyatomic ions with rare earth elements in inductively coupled plasma mass spectrometry by combining algebraic correction with chromatographic separation

A simple and effective procedure is developed to avoid the spectral interference from light rare earth elements (REEs) and barium polyatomic ions on some rare earth elements in inductively coupled plasma mass spectrometry (ICP-MS) by combining algebraic correction with AG50W-×8 cation exchangeable chromatography. Algebraic correction is made to reduce the spectroscopic overlap interference of ¹⁴¹Pr¹⁶O and ¹⁴³Nd¹⁶O on ¹⁵⁷Gd and ¹⁵⁹Tb. The spectroscopic overlap interference of BaO⁺ and BaOH⁺ on some middle REEs are overcome by separation of REEs from barium with AG50W-×8 cation exchangeable chromatography. Prior to the determination, REEs are separated from complicated matrix samples using AG50W-×8 cation exchangeable resin. Ba is eluted with 2 mol/l HNO₃ solution. REEs are retained and could then be eluted with 5 mol/l HNO₃ solution. Recoveries for REEs are from 96 to 110%. More than 99.5% of Ba in the sample is removed, ensuring that the spectral interference from barium polyatomic ions on some middle REEs such as Nd, Sm, Eu and Gd are eliminated. The potential of the proposed method is evaluated by analysis of Certified Reference Materials (CRMs). Results show that experimental data are in good agreement with the certified values. The new technique has been successfully employed for the determination of REEs in practical soil and plant samples.     

Uncertainty propagation through correction methodology for the determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry

Determination of rare earth elements by quadrupole based inductively coupled plasma mass spectrometry (ICP-QMS) shows several spectroscopic overlaps from M⁺, MO⁺ and MOH⁺ ions. Especially, the spectroscopic interferences are observed from the atomic and molecular species of lighter rare earth elements including Ba during the determination of Eu, Gd and Tb. Mathematical correction methods, knowing the at.% abundances of different interfering isotopes, and the extent of formation of molecular species determined experimentally, have been used to account for various spectroscopic interferences. However, the uncertainty propagated through the mathematical correction limits its applicability. The uncertainty propagation increases with the increase in contribution from interfering species. However, for the same extent of total contribution, the overall error decreases when the interfering species are more than one. In this work, chondrite as well as a few geological reference materials containing different proportions of various rare earth elements have been used to study the contributions of different interfering species and the corresponding uncertainty in determining the concentrations of rare earth elements. A number of high abundant isotopes are proposed for determining the concentrations of various rare earth elements. The proposed isotopes are tested experimentally for determining the concentrations of different rare earth elements in two USGS reference materials AGV-1 and G-2. The interferences over those isotopes are corrected mathematically and the uncertainties propagated due to correction methodology are determined for those isotopes. The uncertainties in the determined concentrations of rare earth elements due to interference correction using the proposed isotopes are found to be comparable with those obtained by the commonly used isotopes for various rare earth elements.     

Determination of rare earth elements in environmental matrices by sector-field inductively coupled plasma mass spectrometry

In the framework of an international certification campaign, sector-field inductively coupled plasma mass spectrometry (sector-field ICP–MS) was used for the accurate determination of the rare earth elements in five candidate reference materials: aquatic plant, calcareous soil, mussel tissue, river sediment, and tuna muscle. All samples were taken into solution by use of microwave-assisted or mixed microwave-assisted / open beaker acid digestion. Subsequently, the samples were appropriately diluted and subjected to ICP–MS analysis. Except for Sc, all the elements involved were determined at low mass resolution (R = 300). For Sc, application of a higher resolution setting (R = 3000) was required to separate the analyte signal from those of several molecular ions which gave rise to spectral overlap at low mass resolution. Some of the heavier REE can also suffer from spectral overlap attributed to the occurrence of oxide ions (MO⁺) of the lighter REE and Ba. This spectral overlap could be successfully overcome by mathematical correction. Matrix effects were overcome by use of two carefully selected internal standards, such that external calibration could be used. On each occasion, a geological reference material was analyzed as a quality-control sample and the reliability of all results obtained was additionally checked by means of chondrite normalization. For tuna muscle the content of all REE was below the limit of detection. For calcareous soil and river sediment, low to sub μg g^–1 values were observed, whereas the REE content of aquatic plant and mussel tissue was considerably lower (low to sub ng g^–1). Overall, the results obtained were in excellent agreement with the average values, calculated on the basis of all “accepted” values, obtained in different laboratories using different techniques.     

Determination of Rare Earth Elements in Garnet Minerals,Geological Materials by Inductively Coupled Plasma–Atomic Emission Spectral and Mass Spectral Analysis

Abstract

The performance of inductively coupled plasma–atomic emission spectrometry (ICP‐AES) for the determination of 14 lanthanides and Yttrium was evaluated by comparison with inductively coupled plasma–mass spectral (ICP‐MS) analysis. The geochemical reference samples (GRS), DNC‐1(diabase), AGV‐1(andesite), Sy‐2(syenite), MRG‐1(gabbro), AN‐G(anorthosite), AC‐E(granite), and MAG‐1(marine mud) were chosen as test materials and analyzed for checking the precision and reproducibility of the methods. The mineral garnet is separated from the black sands of the southwest coast of India, and the combined cation exchange–ICP method of AES analysis and MS analysis were carried out for the determination of rare earth elements. Both techniques are within the requirements needed for garnet minerals. The determination of rare‐earth elements in these minerals, which contain other elements as major contribution and trace distribution of rare‐earth elements, shows that ICP applied under the proper working condition lives up to the expectations. Major element analysis gives the formula of garnet of Manavalakurichi (MK) as (FeCaMg)_2.79Al_2.07Si_3.05O₁₂ approximated to Fe₃Al₂Si₃O₁₂, hence of almandine-type garnet. The enrichment of heavy lanthanides compared to the light lanthanides indicates that these lanthanides occupy the coordinaton site of Fe²⁺ by replacement. Both techniques are excellent in determining the very low concentration of lanthanides in geological materials, specifically garnet.     

Lanthanide Crownphthalocyaninates: Synthesis,Structure, and Peculiarities of Formation

Complexing properties of lanthanide ions with respect to crown-substituted phthalocyanine are analyzed. Complexes of lanthanides (La, Nd, Sm, Eu, Gd, Tb, Yb, Lu, Y) with tetra-15-crown-5-phthalocyanine are synthesized and their structures are studied by photoelectronic, IR, ¹H NMR, and mass spectrometry methods.     

Luminescence Tuning and White‐Light Emission of Co‐doped Ln–Cd–Organic Frameworks

Four new three‐dimensional isostructural lanthanide–cadmium metal–organic frameworks (Ln–Cd MOFs), [LnCd₂(imdc)₂(Ac)(H₂O)₂]?H₂O (Ln=Pr ( 1 ), Eu ( 2 ), Gd ( 3 ), and Tb ( 4 ); H₃imdc=4,5‐imidazoledicarboxylic acid; Ac=acetate), have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, inductively coupled plasma (ICP) analysis, and X‐ray diffraction. Single‐crystal X‐ray diffraction shows that two Ln^III ions are surrounded by four Cd^II ions to form a heteronuclear building block. The blocks are further linked to form 3D Ln–Cd MOFs by the bridging imdc^3? ligand. Furthermore, the left‐ and right‐handed helices array alternatively in the lattice. Eu–Cd and Tb–Cd MOFs can emit characteristic red light with the Eu^III ion and green light with the Tb^III ion, respectively, while both Gd–Cd and Pr–Cd MOFs generate blue emission when they are excited. Different concentrations of Eu³⁺ and Tb³⁺ ions were co‐doped into Gd–Cd/Pr–Cd MOFs, and tunable luminescence from yellow to white was achieved. White‐light emission was obtained successfully by adjusting the excitation wavelength or the co‐doping ratio of the co‐doped Gd–Cd and Pr–Cd MOFs. These results show that the relative emission intensity of white light for Gd–Cd:Eu³⁺,Tb³⁺ MOFs is stronger than that of Pr–Cd:Eu³⁺,Tb³⁺ MOFs, which implies that the Gd complex is a better matrix than the Pr complex to obtain white‐light emission materials.     

A Revised Periodic Table: With the Lanthanides Repositioned

The lanthanide elements from lanthanum to lutetium inclusive are incorporated into the body of the periodic table. They are subdivided into three sub-groups according to their important oxidation states: La to Sm, Eu to Tm, Yb and Lu, so that Eu and Yb fall directly below Ba; La, Gd, Lu form a column directly below Y; Ce and Tb fall in a vertical line between Zr and Hf. Pm falls below Tc; both are radioactive, and not naturally occurring. The elements with easily attained 2⁺ and 4⁺ oxidation states are grouped and clearly differentiated. Gadolinium has an important position as the centre of four triads in the block of elements that surround it– La, Gd, Lu; Ba, Gd, Hf; Eu, Gd, Tb; Yb, Gd, Ce. This new arrangement has the advantages of compactness, simplicity and clarity – there are no tie lines; and important oxidation states of these metals are emphasized. The actinides are also accommodated within this system, and element 114 falls naturally below lead in Group 14.     

4-Nitro and 4-chloro pyridine-N-oxide complexes of lanthanide perchlorates

Adducts of lanthanide perchlorates with 4-nitro and 4-chloro pyridine-Noxides (4-NPNO and 4-CPNO respectively) have been synthesised for the first time and characterised by analysis, electrolytic conductance, infrared, proton-NMR and electronic spectral data. The complexes are of the compositions Ln₂(NPNO)₁₅ (ClO₄)₆ (Ln = La, Pr, Nd and Gd), Tb(NPNO), (C1O₄)₆), Ln₂(NPNO)₁₃ (C1O₄)₆) (Ln = Dy, Ho, and Yb); Ln (CPNO)₈ (C10₄)₃) (Ln = La, Pr, Nd, Tb, Dy, Ho and Yb) and Ln(CPNO), (C1O₄)₃) (Ln = Sm and Gd). Conductivity and IR data provide evidence for the non-coordinated nature of the perchlorate groups. IR and NMR spectra suggest coordinationvia the oxygen of the N-oxide group. Electronic spectral shapes of the Nd⁺³ and Ho⁺³ complexes are interpreted in terms of eight-and seven-coordinate environments in the case of 4-NPNO complexes and eight-coordination in the case of 4-CPNO complexes. IR data indicate bridged structure in NPNO complexes of lanthanides other than Tb.     

Octanuclear Ni4Ln4 Coordination Aggregates from Schiff Base Anion Supports and Connecting of Two Ni2Ln2 Cubes: Syntheses,Structures, and Magnetic Properties

A family of 3d–4f aggregates have been reported through guiding the dual coordination modes of ligand anion (HL^?) and in situ generated ancillary bridge driven self‐assembly coordination responses toward two different types of metal ions. Reactions of lanthanide(III) nitrate (Ln=Gd, Tb, Dy, Ho and Yb), nickel(II) acetate and phenol‐based ditopic ligand anion of 2‐[{(2‐hydroxypropyl)imino}methyl]‐6‐methoxyphenol (H₂L) in MeCN‐MeOH (3 : 1) mixture and LiOH provided five new octanuclear Ni‐4f coordination aggregates from two Ni₂Ln₂ cubanes. Single‐crystal X‐ray diffraction analysis reveals that all the members of the family are isostructural, with the central core formed from the coupling of two distorted [Ni₂Ln₂O₄] heterometallic cubanes [Ni₂Ln₂(HL)₂(μ₃‐OH)₂(OH)(OAc)₄]⁺ (Ln=Gd ( 1 ), Tb ( 2 ), Dy ( 3 ), Ho ( 4 ) and Yb ( 5 )). Higher coordination demand of 4f ions induced the coupling of the two cubes by (OH)(OAc)₂ bridges. Variable temperature magnetic study reveals weak coupling between the Ni²⁺ and Ln³⁺ ions. For the Tb ( 2 ) and Dy ( 3 ) analogs, the compounds are SMMs without an applied dc field, whereas the Gd ( 1 ) analogue is not an SMM. The observation revealed thus that the anisotropy of the Ln³⁺ ions is central to display the SMM behavior within this structurally intriguing family of compounds.     

Analytical atomic spectroscopy using ion trap devices

Investigations using ion trap devices for analytical atomic spectroscopy purposes have focused on the use of an inductively coupled plasma (ICP) ion source with ion trap mass spectrometric (ITMS) detection. Initial studies were conducted with an instrument assembled by simply appending an ion trap as the detector to a fairly conventional ICP/MS instrument, i.e. leaving an intermediate linear quadrupole between the plasma source and the ion trap. The principal advantages found with this system include the destruction of nearly all problematic and typical ICP/MS polyatomic ions (e.g., ArH⁺, ArO⁺, ArCl⁺, Ar₂⁺, etc) and a dramatic reduction of the primary plasma source ion, Ar⁺. These results prompted the development of a second-generation plasma source ion trap instrument in which direct coupling of the ICP and ion trap has been effected (i.e. no intermediate linear quadrupole); the same performance benefits have been largely preserved. Initial operation of this instrument is described, characterized, and compared to the originally described ICP/ITMS and conventional ICP/MS systems. In addition, experiments aimed at improving ICP/ITMS sensitivity and selectivity using broadband resonance excitation techniques are described. Finally, the potential for laser optical detection of trapped ions for analytical purposes is speculated upon.     

Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides

The chemistry of lanthanides (Ln=La–Lu) is dominated by the low‐valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO₄ and PrO₂⁺ complexes in the gas phase and in a solid noble‐gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented Pr^V oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.     

Near‐field laser ablation inductively coupled plasma mass spectrometry: a novel elemental analytical technique at the nanometer scale

An analytical technique utilizing a near‐field effect (to enhance the incident light energy on the thin tip of an Ag needle) in a laser ablation inductively coupled plasma mass spectrometry (NF‐LA‐ICP‐MS) procedure was developed. To produce the thin needles with a tip diameter in the hundreds of nm range a robust needle etching procedure was established. The ‘sample‐to‐tip’ distance was controlled via the measurement of a tunnel current between the needle and sample surface. The NF‐LA‐ICP‐MS technique thus developed was applied for the analysis of copper isotopic standard reference material NIST SRM 976 and tungsten‐molybdenum alloy NIST SRM 480 in the nm resolution range. The observed craters ranged from 200 nm to about 2 µm in diameter and were dependent on the needle used as well as on the ‘sample‐to‐tip’ distance. The mass spectrometric measurements of ⁶³Cu⁺ ion intensity on NIST SRM 976 showed that using near‐field enhancement in laser ablation allowed a roughly 6‐fold increase in the ion intensity of the analyte when the needle was about 100 nm (and below) from the surface, in contrast to when it was far away (e.g. 10 µm) from the sample. The relative standard deviation (RSD) of the ⁶⁵Cu⁺/⁶³Cu⁺ isotopic ratio measurements by NF‐LA‐ICP‐MS was 3.9% (n = 9). The detection efficiencies obtained for the compared LA‐ICP‐MS and NF‐LA‐ICP‐MS methods were found to be 4.6 * 10^?3 counts per second (cps)/ablated atom and 2.7 * 10^?5 cps/ablated atom, respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Hetero‐tri‐spin [2p‐3d‐4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo‐Ligands: Synthesis,Structure, and Magnetic Properties

Employing nitronyl nitroxide lanthanide(III) complexes as metallo‐ligands allowed the efficient and highly selective preparation of three series of unprecedented hetero‐tri‐spin (Cu?Ln‐radical) one‐dimensional compounds. These 2p–3d–4f spin systems, namely [Ln₃Cu(hfac)₁₁(NitPhOAll)₄] (Ln^III=Gd 1_Gd , Tb 1_Tb , Dy 1_Dy ; NitPhOAll=2‐(4′‐allyloxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide), [Ln₃Cu(hfac)₁₁(NitPhOPr)₄] (Ln^III=Gd 2_Gd , Tb 2_Tb , Dy 2_Dy , Ho 2_Ho , Yb 2_Yb ; NitPhOPr=2‐(4′‐propoxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) and [Ln₃Cu(hfac)₁₁(NitPhOBz)₄] (Ln^III=Gd 3_Gd , Tb 3_Tb , Dy 3_Dy ; NitPhOBz=2‐(4′‐benzyloxyphenyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide) involve O‐bound nitronyl nitroxide radicals as bridging ligands in chain structures with a [Cu‐Nit‐Ln‐Nit‐Ln‐Nit‐Ln‐Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal–radical interactions take place in these hetero‐tri‐spin chain complexes, these and the next‐neighbor interactions have been quantified for the Gd derivatives. Complexes 1_Tb and 2_Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single‐chain magnet behavior.     

Extraction chromatographic separation of carrier-free Tb and Pm generated in (p,xn)-type nuclear reactions

The nuclear reactions of (p, xn)-type, E_p=100–120 MeV, on Gd and Nd have been used to produce highly radioactive preparations of Tb and Pm enriched with neutron-deficient isotopes. Under comparable conditions the yields of practically all isotopes are considerably higher than in Tb and Gd spallation reactions at E_p=660 MeV. The radioactivity of screened¹⁵⁴Tb and¹⁵⁶Tb isotopes has been increased more than 40 times. Tb and Pm were separated from gram amounts of the target-elements by the extraction chromatography technique with undiluted di-(2-ethylhexyl) phosphoric acid as stationary phase. The radiochemical method developed was also applied to separate the radiochemically pure preparation of¹⁶¹Tb from Gd oxide irradiated with thermal neutrons.     

Carbon Nanofibers as Solid‐Phase Extraction Adsorbent for the Preconcentration of Trace Rare Earth Elements and Their Determination by Inductively Coupled Plasma Mass Spectrometry

Abstract

Systematic investigations were carried out into the sorption of rare earth elements (REEs) on carbon nonofibers (CNFs) by inductively coupled plasma mass spectrometry (ICP‐MS). The experimental parameters for preconcentration of REEs, such as pH, sample flow rate and volume, eluent concentration, and interfering ions on preconcentration of REEs have been examined in detail. The studied metal ions can be adsorbed quantitatively on CNFs in a pH range from 2.0 to 5.0, and then eluted completely with 0.5 mol l^?1 HNO₃. Based on the above facts, a novel method using a microcolumn packed with carbon nanofibers as an adsorption material was developed for the separation and preconcentration of REEs prior to their determination by ICP‐MS. The proposed method has been successfully applied to the determination of light (La), medium (Eu and Gd) and heavy (Yb) rare earth elements in real sample with the recovery more than 90%. In order to validate this method, two certified reference materials of tea leaves (GBW 07605) and mussel (GBW 08571) were analyzed, and the determined values are in good agreement with the certified values.     

Picomolar Traces of Americium(III) Introduce Drastic Changes in the Structural Chemistry of Terbium(III): A Break in the “Gadolinium Break”

The crystallization of terbium 5,5′‐azobis[1H‐tetrazol‐1‐ide] (ZT) in the presence of trace amounts (ca. 50 Bq, ca. 1.6 pmol) of americium results in 1) the accumulation of the americium tracer in the crystalline solid and 2) a material that adopts a different crystal structure to that formed in the absence of americium. Americium‐doped [Tb(Am)(H₂O)₇ZT]₂ ZT⋅10 H₂O is isostructural to light lanthanide (Ce–Gd) 5,5′‐azobis[1H‐tetrazol‐1‐ide] compounds, rather than to the heavy lanthanide (Tb–Lu) 5,5′‐azobis[1H ‐tetrazol‐1‐ide] (e.g., [Tb(H₂O)₈]₂ZT₃⋅6 H₂O) derivatives. Traces of Am seem to force the Tb compound into a structure normally preferred by the lighter lanthanides, despite a 10⁸‐fold Tb excess. The americium‐doped material was studied by single‐crystal X‐ray diffraction, vibrational spectroscopy, radiochemical neutron activation analysis, and scanning electron microcopy. In addition, the inclusion properties of terbium 5,5′‐azobis[1H‐tetrazol‐1‐ide] towards americium were quantified, and a model for the crystallization process is proposed.     

HPLC‐DAD and HPLC‐ESI‐MS separation,determination and identification of the spin‐labeled diastereoisomers of podophyllotoxin

Spin‐labeled nitroxide derivatives of podophyllotoxin had better antitumor activity and less toxicity than that of the parent compounds. However, the 2‐H configurations of these spin‐labeled derivatives cannot be determined by nuclear magnetic resonance (NMR) methods. In the present paper, a high‐performance liquid chromatography‐diode array detection (HPLC‐DAD) and a high‐performance liquid chromatography‐electrospray ionization tandem mass spectrometry (HPLC‐ESI/MS/MS) method were developed and validated for the separation, identification of four pairs of diastereoisomers of spin‐labeled derivatives of podophyllotoxin at C‐2 position. In the HPLC‐ESI/MS spectra, each pair of diastereoisomers of the spin‐labeled derivatives in the mixture was directly confirmed and identified by [M+H]⁺ ions and ion ratios of relative abundance of [M‐ROH+H]⁺ (ion 397) to [M+H]⁺. When the [M‐ROH+H]⁺ ions (at m/z 397) were selected as the precursor ions to perform the MS/MS product ion scan. The product ions at m/z 313, 282, and 229 were the common diagnostic ions. The ion ratios of relative abundance of the [M‐ROH+H]⁺ (ion 397) to [M+H]⁺, [A+H]⁺ (ion 313) to [M‐ROH+H]⁺, [A+H‐OCH₃]⁺ (ion 282) to [M‐ROH+H]⁺ and [M‐ROH‐ArH+H]⁺ (ion 229) to [M‐ROH+H]⁺ of each pair of diastereoisomers of the derivatives specifically exhibited a stereochemical effect. Thus, by using identical chromatographic conditions, the combination of DAD and MS/MS data permitted the separation and identification of the four pairs of diastereoisomers of spin‐labeled derivatives of podophyllotoxin at C‐2 in the mixture.     

Crystal and Electronic Structures of the New Carbomolybdates(III), RE2[Mo2C3] with RE = Ce,Sm, Tb,and Dy

Four new ternary carbometalates of the general formula RE₂[Mo₂C₃] with RE = Ce, Sm, Tb and Dy have been prepared by a high temperature synthesis route. The Ce, Tb and Dy compounds crystallize isotypic to Er₂[Mo₂C₃], Sm₂[Mo₂C₃], however, is an isotype of Ho₂[Cr₂C₃]. The crystal structures comprise polyanionic layers [(Mo₂C₃)^6?] with the rare‐earth metal ions in between. The layers are constructed by edge and vertex connected MoC₄ tetrahedra, which display strong covalent Mo–C bonds. The compounds show metallic behaviour close to the classical limit of 100 μΩ cm for metallic conductors. The magnetic properties are quite different, however they are consistent with the presence of trivalent RE³⁺ ions with the exception of Ce₂[Mo₂C₃], which contains nonmagnetic Ce species. Electronic structure calculations reveal that the additional electron mainly populates the Ce partial structure. The title compounds extend the series of known carbomolybdates RE₂[Mo₂C₃]. The late lanthanides Gd, Tb, Dy, Ho, Er, Tm, and Lu with comparatively small RE³⁺ ions and Ce as Ce⁴⁺ adopt the Er₂[Mo₂C₃] structure type, whereas the early lanthanides Sm and Pr with larger RE³⁺ ions crystallize in the structure types of Ho₂[Cr₂C₃] and Pr₂[Mo₂C₃], respectively.