The structure and bonding of a Pr‐doped boron cluster (PrB7−) are investigated using photoelectron spectroscopy and quantum chemistry. The adiabatic electron detachment energy of PrB7−is found to be low [1.47(8) eV]. A large energy gap is observed between the first and second detachment features, indicating a highly stable neutral PrB7. Global minimum searches and comparison between experiment and theory show that PrB7−has a half‐sandwich structure with C6vsymmetry. Chemical bonding analyses show that PrB7−can be viewed as a PrII[η7‐B73−] complex with three unpaired electrons, corresponding to a Pr (4f26s1) open‐shell configuration. Upon detachment of the 6s electron, the neutral PrB7cluster is a highly stable PrIII[η7‐B73−] complex with Pr in its favorite +3 oxidation state. The B73−ligand is found to be highly stable and doubly aromatic with six delocalized π and six delocalized σ electrons and should exist for a series of lanthanide MIII[η7‐B73−] complexes.
Lanthanide (Ln) elements are generally found in the oxidation state +II or +III, and a few examples of +IV and +V compounds have also been reported. In contrast, monovalent Ln(+I) complexes remain scarce. Here we combine photoelectron spectroscopy and theoretical calculations to study Ln-doped octa-boron clusters (LnB8−, Ln = La, Pr, Tb, Tm, Yb) with the rare +I oxidation state. The global minimum of the LnB8−species changes from
- Award ID(s):
- 2053541
- NSF-PAR ID:
- 10307078
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 12
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Metalation of the polynucleating ligandF,tbsLH6(1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2affords the dinuclear product (F,tbsLH2)Zn2(
1 ), which can be further deprotonated to yield (F,tbsL)Zn2Li2(OEt2)4(2 ). Transmetalation of2 with NiCl2(py)2yields the heterometallic, trinuclear cluster (F,tbsL)Zn2Ni(py) (3 ). Reduction of3 with KC8affords [KC222][(F,tbsL)Zn2Ni] (4 ) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to4 generates the bridging μ3‐nitrenoid adduct [K(THF)3][(F,tbsL)Zn2Ni(μ3‐NAd)] (5 ). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state (S =). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K2(THF)9][(F,tbsL)Zn2Ni(μ3‐NAd)] (6 ) was isolated and characterized while the neutral redox isomer was observed to undergo both intra‐ and intermolecular H‐atom abstraction processes. Ni K‐edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn2Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for5 . -
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Abstract Metalation of the polynucleating ligandF,tbsLH6(1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2affords the dinuclear product (F,tbsLH2)Zn2(
1 ), which can be further deprotonated to yield (F,tbsL)Zn2Li2(OEt2)4(2 ). Transmetalation of2 with NiCl2(py)2yields the heterometallic, trinuclear cluster (F,tbsL)Zn2Ni(py) (3 ). Reduction of3 with KC8affords [KC222][(F,tbsL)Zn2Ni] (4 ) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to4 generates the bridging μ3‐nitrenoid adduct [K(THF)3][(F,tbsL)Zn2Ni(μ3‐NAd)] (5 ). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state (S =). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K2(THF)9][(F,tbsL)Zn2Ni(μ3‐NAd)] (6 ) was isolated and characterized while the neutral redox isomer was observed to undergo both intra‐ and intermolecular H‐atom abstraction processes. Ni K‐edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn2Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for5 . -
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Abstract Exploration of the reduction chemistry of the 2,2’‐bipyridine (bipy) lanthanide metallocene complexes Cp*2LnCl(bipy) and Cp*2Ln(bipy) (Cp* = C5Me5) resulted in the isolation of a series of complexes with unusual composition and structure including complexes with a single Cp* ligand, multiple azide ligands, and bipy ligands with close parallel orientations. These results not only reveal new structural types, but they also show the diverse chemistry displayed by this redox‐active platform. Treatment of Cp*2NdCl(bipy) with excess KC8resulted in the formation of the mono‐Cp* Nd(III) complex, [K(crypt)]2[Cp*Nd(bipy)2],
1 , as well as [K(crypt)][Cp*2NdCl2],2 , and the previously reported [K(crypt)][Cp*2Nd(bipy)]. A mono‐Cp* Lu(III) complex, Cp*Lu(bipy)2,3 , was also found in an attempt to make Cp*2Lu(bipy) from LuCl3, 2 equiv. of KCp*, bipy, and K/KI. Surprisingly, the (bipy)1−ligands in neighboring molecules in the structure of3 are oriented in a parallel fashion with intermolecular C⋅⋅⋅C distances of 3.289(4) Å, which are shorter than the sum of van der Waals radii of two carbon atoms, 3.4 Å. Another product with one Cp* ligand per lanthanide was isolated from the reaction of [K(crypt)][Cp*2Eu(bipy)] with azobenzene, which afforded the dimeric Eu(II) complex, [K(crypt)]2[Cp*Eu(THF)(PhNNPh)]2,4 . Attempts to make4 from the reaction between Cp*2Eu(THF)2and a reduced azobenzene anion generated instead the mixed‐valent Eu(III)/Eu(II) complex, [K(crypt)][Cp*Eu(THF)(PhNNPh)]2,5 , which allows direct comparison with the bimetallic Eu(II) complex4 . Mono‐Cp* complexes of Yb(III) are obtained from reactions of the Yb(II) complex, [K(crypt)][Cp*2Yb(bipy)], with trimethylsilylazide, which afforded the tetra‐azido [K(crypt)]2[Cp*Yb(N3)4],6 , or the di‐azido complex [K(crypt)]2[Cp*Yb(N3)2(bipy)],7 a , depending on the reaction stoichiometry. A mono‐Cp* Yb(III) complex is also isolated from reaction of [K(crypt)][Cp*2Yb(bipy)] with elemental sulfur which forms the mixed polysulfido Yb(III) complex [K(crypt)]2[Cp*Yb(S4)(S5)],8 a . In contrast to these reactions that form mono‐Cp* products, reduction of Cp*2Yb(bipy) with 1 equiv. of KC8in the presence of 18‐crown‐6 resulted in the complete loss of Cp* ligands and the formation of [K(18‐c‐6)(THF)][Yb(bipy)4],9 . The (bipy)1−ligands of9 are arranged in a parallel orientation, as observed in the structure of3 , except in this case this interaction is intramolecular and involves pairs of ligands bound to the same Yb atom. Attempts to reduce further the Sm(II) (bipy)1−complex, Cp*2Sm(bipy) with 2 equiv. of KC8in the presence of excess 18‐crown‐6 led to the isolation of a Sm(III) salt of (bipy)2−with an inverse sandwich Cp* counter‐cation and a co‐crystallized K(18‐c‐6)Cp* unit, [K2(18‐c‐6)2Cp*]2[Cp*2Sm(bipy)]2 ⋅ [K(18‐c‐6)Cp*],10 . -
null (Ed.)Two efficient lanthanide ion sensitizers 2,6-bis(oxazoline)-4-phenyl-pyridine (PyboxPh, 1 ) and 2,6-bis(oxazoline)-4-thiophen-2-yl-pyridine (Pybox2Th, 2 ) were synthesized. 1 crystallizes in the monoclinic space group P 21/ c with cell parameters a = 16.3794(4) Å, b = 7.2856(2) Å, c = 11.7073(3) Å, β = 97.229(1)° and V = 1385.97(6) Å 3 . 2 crystallizes in the monoclinic space group P 21/ n with cell parameters a = 5.9472(2), b = 16.0747(6), c = 14.3716(5) Å, β = 93.503(1)° and V = 1371.35(8) Å 3 . Photophysical characterization of 1 shows that its triplet state energy is located at 22 250 cm −1 and efficient energy transfer is observed for Eu III and Tb III . Solutions of [Ln(PyboxPh) 3 ] 3+ in dichloromethane display an emission efficiency of 37.2% for LnEu and 24.0% for LnTb. The excited state lifetimes for Eu III and Tb III are 2.227 ms and 723 μs, respectively. The triplet state energy of 2 is located at 19 280 cm −1 and is therefore too low to efficiently sensitize Tb III emission. However, the sensitization of Eu III is effective, with an emission quantum yield of 14.5% and an excited state lifetime of 714 μs. This shows that the derivatization of the chelator is strongly influenced by the aromatic substituents on the para -position of the pyridine ring. New isostructural 1 : 1 complexes of PyboxPh with Eu III ( 3 ) and Tb III ( 4 ) were also isolated and crystallize in the triclinic space group P 1̄ with cell parameters a = 9.1845(2) Å, b = 10.3327(2) Å, c = 11.9654(2) Å, α = 98.419(1)°, β = 108.109(1)°, γ = 91.791(1)°, V = 1064.08(4) Å 3 and a = 7.8052(1) Å, b = 11.8910(1) Å, c = 14.2668(2) Å, α = 72.557(1)°, β = 86.355(1)°, γ = 77.223(1)°, V = 1231.95(3) Å 3 , respectively.more » « less
