Structural characterization of the ionic title complex, [MgBr(THF)5][Co(dpbz)2]·2THF [THF is tetrahydrofuran, C4H8O; dpbz is 1,2-bis(diphenylphosphanyl)benzene, C30H24P2], revealed a well-separated cation and anion co-crystallized with two THF solvent molecules that interact with the cation via weak C—H...O contacts. The geometry about the cobalt center is pseudotetrahedral, as is expected for a d10 metal center, only deviating from an ideal tetrahedral geometry because of the restrictive bite angles of the bidentate phosphane ligands. Three THF ligands of the cation and one co-crystallized THF solvent molecule are each disordered over two orientations. In the extended structure, the cations and THF solvent molecules are arranged in (100) sheets that alternate with layers of anions, the latter of which show various π-interactions, which may explain the particular packing arrangement.
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Crystal structure of bromidopentakis(tetrahydrofuran-κ O )magnesium bis[1,2-bis(diphenylphosphanyl)benzene-κ 2 P , P ′]cobaltate(−1) tetrahydrofuran disolvate
Structural characterization of the ionic title complex, [MgBr(THF) 5 ][Co(dpbz) 2 ]·2THF [THF is tetrahydrofuran, C 4 H 8 O; dpbz is 1,2-bis(diphenylphosphanyl)benzene, C 30 H 24 P 2 ], revealed a well-separated cation and anion co-crystallized with two THF solvent molecules that interact with the cation via weak C—H...O contacts. The geometry about the cobalt center is pseudotetrahedral, as is expected for a d 10 metal center, only deviating from an ideal tetrahedral geometry because of the restrictive bite angles of the bidentate phosphane ligands. Three THF ligands of the cation and one co-crystallized THF solvent molecule are each disordered over two orientations. In the extended structure, the cations and THF solvent molecules are arranged in (100) sheets that alternate with layers of anions, the latter of which show various π-interactions, which may explain the particular packing arrangement.
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- Award ID(s):
- 1725028
- NSF-PAR ID:
- 10094488
- Date Published:
- Journal Name:
- Acta Crystallographica Section E Crystallographic Communications
- Volume:
- 75
- Issue:
- 2
- ISSN:
- 2056-9890
- Page Range / eLocation ID:
- 304 to 307
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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 .
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1107/S2056989019001671
