Synthesis and structure of cationic guanidinate-bridged bimetallic {Li7M} cubes (M = Mn, Co, Zn) with inverse crown counter anions

Woodruff, Daniel N.; Bodensteiner, Michael; Sells, Daniel O.; Winpenny, Richard E. P.; Layfield, Richard A.

doi:10.1039/c1dt10999e

Cited by 9 publications

(2 citation statements)

References 70 publications

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“…The 1 H NMR spectrum of 1 recorded in toluene-D 8 confirms the presence of the Cp ligand (δ = 23.41 ppm); however, a sharp resonance at δ = 1.55 ppm and a broad resonance at 2.85 ppm, likely due to the trimethylsilyl groups, were also observed (Supporting Information, Figure S2). The 7 Li NMR spectrum of 1 in toluene-D 8 (Supporting Information, Figure S3) features a weak, broad resonance with a chemical shift of δ = 140.3 ppm: this is substantially downfield relative to the 7 Li chemical shifts reported for [Li{N(SiMe 3 ) 2 }] in various solvents and at various concentrations, which are typically in the range of δ ≈ ± 1 ppm . The position and appearance of 7 Li resonance in particular suggests that a paramagnetic lithium-containing complex is present in solution, although there is no direct evidence to suggest that the solid-state structure of 1 is preserved in toluene solution.…”

Section: Synthesis and Structures Of 1–3mentioning

confidence: 95%

Transmetalation of Chromocene by Lithium-Amide, -Phosphide, and -Arsenide Nucleophiles

Scheuermayer

Tuna²,

Moreno‐Pineda³

et al. 2013

Inorg. Chem.

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The pnictogen-centered nucleophiles LiE(SiMe3)2 (E = N, P, or As) substitute a cyclopentadienide ligand of chromocene (Cp2Cr), with elimination of lithium cyclopentadienide, to give the series of pnictogen-bridged compounds [(μ:η(2):η(5)-Cp)Cr{μ-N(SiMe3)2}2Li] (1) and [(η(5)-Cp)Cr{μ-E(SiMe3)2}]2, with E = P (2) or E = As (3). Whereas 1 is a heterobimetallic coordination polymer, 2 and 3 are homometallic dimers, with the differences being due to a structure-directing influence of the hard or soft character of the bridging group 15 atoms. For compound 1, the experimental magnetic susceptibility data were accurately reproduced by a single-ion model based on high-spin chromium(II) (S = 2), which gave a g-value of 1.93 and an axial zero-field splitting parameter of D = -1.83 cm(-1). Determinations of phosphorus- and arsenic-mediated magnetic exchange coupling constants, J, are rare: in the dimers 2 and 3, variable-temperature magnetic susceptibility measurements identified strong antiferromagnetic exchange between the chromium(II) centers, which was modeled using the spin Hamiltonian H = -2J(S(CrA)·S(CrB)), and produced large coupling constants of J = -166 cm(-1) for 2 and -77.5 cm(-1) for 3.

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Section: Synthesis and Structures Of 1–3mentioning

confidence: 95%

Transmetalation of Chromocene by Lithium-Amide, -Phosphide, and -Arsenide Nucleophiles

Scheuermayer

Tuna²,

Moreno‐Pineda³

et al. 2013

Inorg. Chem.

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“…58 The reactions of [Li 3 (m-HMDS) 2 (m-,m-hpp)] with MnCl 2 , CoCl 2 or ZnBr 2 have resulted in the formation of the separated ion-pairs [MLi 7 (m 8 -O)(m-,m-hpp) 6 ] + [A] À , in which the counter anion is the inverse crown [{Li(m-HMDS)} 5 (m 5 -Cl)] À . 59 The synthesis and characterisation of lithium cyanate, LiOCN, have been reported. 60 The plastic crystallinity of [LiB(OCH 2-CH 2 OCH 3 ) 4 ] has been described.…”

Section: Group 16 Donor Ligandsmentioning

confidence: 99%

Alkaline and alkaline earth metals

Hill

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Advances made during the calendar year 2011 relating to the coordination and inorganic chemistry of the elements of Groups 1 and 2 are summarised in this non-critical review. Coverage concentrates on topics centred around the synthesis, and applications of coordination and organometallic compounds of these elements. HighlightsThe isolation and reaction chemistry of kinetically-stabilised Group 2 species in which the alkaline earth centre exists in a formal +1 oxidation state has received intense international attention while interest in the potential of alkaline earth complexes as benign and inexpensive reagents for catalysis has continued to develop. LithiumA review of the resting-state structures of organocuprates determined using X-ray crystallography has appeared. 1 The electronic stability of s-block benzylates and di-and tri-phenylmethanide derivatives has been reviewed. 2 Reactions of the lithium boryl LiB(DippNCHQCHNDipp) with organohalides (RX) giving RB(DippNCHQCHNDipp) have been studied using DFT calculations. 3 Group 14 donor ligands An X-ray diffraction analysis of tetrareduced corannulene, C 20 H 10 4À , has confirmed the formation of a sandwich-type supramolecular aggregate in which five Li + ions are sandwiched between the two tetrareduced corannulene decks. 4 A combined experimental and DFT study has predicted that benzyl anions with strong p-withdrawing groups in the meta position have low energy diradical or triplet electronic states. 5 A lithium complex of an abnormal carbene with the composition [H 3 BC{{N(2, Pr 2 )C 6 H 3 } 2 )CHCLi(THF) 3 }] has been synthesised by lithiation of the NHC borane adduct. 6 Diastereomeric oxazolinylaziridines (R,R)-9 and (R,S)-9 have been regioselectively lithiated at the a-position with respect to the oxazolinyl ring. 7 Computational studies of the carbolithiation of b-methylstyrene with

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