Dominance of Cyclobutadienyl Over Cyclopentadienyl in the Crystal Field Splitting in Dysprosium Single-Molecule Magnets.

Replacing a monoanionic cyclopentadienyl (Cp) ligand in dysprosium single-molecule magnets (SMMs) with a dianionic cyclobutadienyl (Cb) ligand in the sandwich complexes [(η4 -Cb'''')Dy(η5 -C5 Me4 t Bu)(BH4 )]- (1), [(η4 -Cb'''')Dy(η8 -Pn† )K(THF)] (2) and [(η4 -Cb'''')Dy(η8 -Pn† )]- (3) leads to larger energy barriers to magnetization reversal (Cb''''=C4 (SiMe3 )4 , Pn† =1,4-di(tri-isopropylsilyl)pentalenyl). Short distances to the Cb'''' ligands and longer distances to the Cp ligands in 1-3 are consistent with the crystal field splitting being dominated by the former. Theoretical analysis shows that the magnetic axes in the ground Kramers doublets of 1-3 are oriented towards the Cb'''' ligands. The theoretical axiality parameter and the relative axiality parameter Z and Zrel are introduced to facilitate comparisons of the SMM performance of 1-3 with a benchmark SMM. Increases in Z and Zrel when Cb''' replaces Cp signposts a route to SMMs with properties that could surpass leading systems.

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

The discovery of materials capable of storing magnetic information at the level of single molecules and even single atoms has fueled renewed interest in the slow magnetic relaxation properties of single-molecule magnets (SMMs). The lanthanide elements, especially dysprosium, continue to play a pivotal role in the development of potential nanoscale applications of SMMs, including, for example, in molecular spintronics and quantum computing. Aside from their fundamentally fascinating physics, the realization of functional materials based on SMMs requires significant scientific and technical challenges to be overcome. In particular, extremely low temperatures are needed to observe slow magnetic relaxation, and while many SMMs possess a measurable energy barrier to reversal of the magnetization ( Ueff), very few such materials display the important properties of magnetic hysteresis with remanence and coercivity. Werner-type coordination chemistry has been the dominant method used in the synthesis of lanthanide SMMs, and most of our knowledge and understanding of these materials is built on the many important contributions based on this approach. In contrast, lanthanide organometallic chemistry and lanthanide magnetochemistry have effectively evolved along separate lines, hence our goal was to promote a new direction in single-molecule magnetism by uniting the nonclassical organometallic synthetic approach with the traditionally distinct field of molecular magnetism. Over the last several years, our work on SMMs has focused on obtaining a detailed understanding of why magnetic materials based on the dysprosium metallocene cation building block {Cp2Dy}+ display slow magnetic relaxation. Specifically, we aspired to control the SMM properties using novel coordination chemistry in a way that hinges on key considerations, such as the strength and the symmetry of the crystal field. In establishing that the two cyclopentadienyl ligands combine to provide a strongly axial crystal field, we were able to propose a robust magneto-structural correlation for understanding the properties of dysprosium metallocene SMMs. In doing so, a blueprint was established that allows Ueff and the magnetic blocking temperature ( TB) to be improved in a well-defined way. Although experimental discoveries with SMMs occur more rapidly than quantitative theory can (currently) process and explain, a clear message emanating from the literature is that a combination of the two approaches is most effective. In this Account, we summarize the main findings from our own work on dysprosium metallocene SMMs, and consider them in the light of related experimental studies and theoretical interpretations of related materials reported by other protagonists. In doing so, we aim to contribute to the nascent and healthy debate on the nature of spin dynamics in SMMs and allied molecular nanomagnets, which will be crucial for the further advancement of this vibrant research field.

Rare-Earth Cyclobutadienyl Sandwich Complexes: Synthesis, Structure and Dynamic Magnetic Properties.

The potassium cyclobutadienyl [K2 {η4 -C4 (SiMe3 )4 }] (1) reacts with MCl3 (THF)3.5 (M=Y, Dy) to give the first rare-earth cyclobutadienyl complexes, that is, the complex anions [M{η4 -C4 (SiMe3 )4 }{η4 -C4 (SiMe3 )3 -κ-(CH2 SiMe2 }]2- , (2M ), as their dipotassium salts. The tuck-in alkyl ligand in 2M is thought to form through deprotonation of the "squarocene" complexes [M{η4 -C4 (SiMe3 )4 }2 ]- by 1. Complex 2Dy is a single-molecule magnet, but with prominent quantum tunneling. An anisotropy barrier of 323(22) cm-1 was determined for 2Dy in an applied field of 1 kOe, and magnetic hysteresis loops were observed up to 7 K.

A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit.

Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt )2 DyCl] (1Dy Cpttt =1,2,4-tri(tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt )2 Dy]+ (2Dy ) as a salt of the non-coordinating [B(C6 F5 )4 ]- anion. Magnetic measurements reveal that [2Dy ][B(C6 F5 )4 ] is an SMM with a record anisotropy barrier up to 1277 cm-1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low-lying Kramers doublets correspond to a well-defined MJ value, with no significant mixing even in the higher doublets.

Iron- and Cobalt-Catalyzed Synthesis of Carbene Phosphinidenes.

In the presence of stoichiometric or catalytic amounts of [M{N(SiMe3 )2 }2 ] (M=Fe, Co), N-heterocyclic carbenes (NHCs) react with primary phosphines to give a series of carbene phosphinidenes of the type (NHC)⋅PAr. The formation of (IMe4 )⋅PMes (Mes=mesityl) is also catalyzed by the phosphinidene-bridged complex [(IMe4 )2 Fe(µ-PMes)]2 , which provides evidence for metal-catalyzed phosphinidene transfer.

Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN](.-) . The [HAN](.-) radical can be transferred to the cobalt(II) amide [Co{N(SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N'')2 }3 ]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt-ligand antiferromagnetic exchange and J≈-290 cm(-1) (-2 J formalism). In contrast, the Co(II) centres in the unreduced analogue [(HAN){Co(N'')2 }3 ] are weakly coupled (J≈-4.4 cm(-1) ). The finding that [HAN](.-) can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.

Carbene rearrangements in three-coordinate N-heterocyclic carbene complexes of cobalt(II) bis(trimethylsilyl)amide.

The synthesis and molecular structures of the cobalt(II) N-heterocyclic carbene (NHC) complexes [(NHC)Co{N(SiMe3)2}2], where NHC = 1,3-bis(diisopropylphenyl)imidazolylidene (IPr) (6), 1,3-bis(mesityl)imidazolylidene (IMes) (7), and 1,3-bis(tert-butyl)imidazol-2-ylidene (I(t)Bu) (8), are reported. Complexes 6-8 are rare examples of three-coordinate cobalt NHC complexes. The steric congestion within the coordination environments of the cobalt(II) centers in 6 and 7 results in the longest Co-C(NHC) distances currently known. Investigating the thermal stability of 6-8, we have found that the steric congestion in 6 is such that heating the complex to reflux in toluene prompts a rearrangement from the normal, C2-bonding mode of the IPr ligand to the corresponding "abnormal" or mesoionic bonding mode. The rearrangement results in formation of [(aIPr)Co{N(SiMe3)2}2] (9), which is the first cobalt complex of an abnormal NHC ligand. The Co-C bond in 9 is 0.06 Å shorter than the analogous bond in 6, suggesting that, although the rearrangement occurs due to the spatial demands of the IPr ligand, there is also a thermodynamic driving force in terms of the Co-C bond. In contrast to the case for 6, complex 7 is stable with respect to the normal-to-abnormal rearrangement. Refluxing complex 8 in toluene results in activation of a tert-butyl substituent, which is eliminated as isobutene, followed by formation of the 1-tert-butylimidazole complex [((t)BuIm)Co{N(SiMe3)2}2] (10).

Low-coordinate bismuth cations.

Chloride abstraction from the diamido-bismuth compound Bi(Me2Si{NAr}2)Cl (1, Ar = 2,6-i-Pr2C6H3) using MCl3 (M = Al, Ga) is a facile route to cationic species. Stoichiometric reactions afford the tetrachlorometallate salts [Bi(Me2Si{NAr}2)][MCl4] (2a, M = Al; 3a, M = Ga), whereas reaction with 0.5 equiv of the group 13 reagent gives the µ-chlorido bridged cations [{Bi(Me2Si{NAr}2)}2(µ-Cl)][MCl4] (2b, M = Al; 3b, M = Ga). The crystal structure of 2a shows a formally two-coordinate bismuth cation, with a Bi···Cl contact to the [AlCl4](-) anion, whereas the structure of 3b shows a total of three Bi···Cl contacts to [GaCl4](-). Both species associate as {1:1}2 dimers in the solid state through additional Bi···Cl interactions. Attempted preparation of cationic complexes using either NaBR4 (R = Ph, Et) or [HNEt3][BPh4] were unsuccessful. Instead of forming the borate salts, the neutral compounds Bi(Me2Si{NAr}2)R (4, R = Et; 5, R = Ph) were isolated as a result of aryl/alkyl transfer from boron to bismuth.

Normal-to-abnormal rearrangement and NHC activation in three-coordinate iron(II) carbene complexes.

The 'normal' three-coordinate iron-NHC complex [(IPr)Fe(N'')2] (N″ = N(SiMe3)2) rearranges to its abnormal NHC analogue [(aIPr)Fe(N″)2] (6) on heating, providing a rare abnormal iron-aNHC complex, and the first such three-coordinate complex. The tert-butyl-substituted complex [(I(t)Bu)Fe(N″)2] (4) undergoes a thermal decomposition that has not previously been observed in iron-NHC chemistry, resulting in the bis(imidazole) complex [((t)BuIm)2Fe(N″)2] (7). A mechanism that involves consecutive C-H and C-N activation is proposed to account for the formation of 7.

Single-molecule magnet properties of a monometallic dysprosium pentalene complex.

The pentalene-ligated dysprosium complex [(η8-Pn†)Dy(Cp*)] (1Dy) (Pn† = [1,4-(iPr3Si)2C8H4]2-) and its magnetically dilute analogue are single-molecule magnets, with energy barriers of 245 cm-1. Whilst the [Cp*]- ligand in 1Dy provides a strong axial crystal field, the overall axiality of this system is attenuated by the unusual folded structure of the [Pn†]2- ligand.

Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet.

Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(Cp i Pr5)Dy(Cp*)]+ (Cp i Pr5, penta-iso-propylcyclopentadienyl; Cp*, pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of U eff = 1541 wave number is also measured. The magnetic blocking temperature of T B = 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.

Activation of C-H bonds by rare-earth metallocene-butyl complexes.

The stable metallocene-butyl complexes [(CpMe)2M(nBu)]2 (M = Y, Dy) were synthesized and their reactivity towards to ferrocene and bulky N-heterocyclic carbenes investigated. Selective mono-deprotonation of ferrocene and a benzylic methyl group of IMes were observed, whereas a control reaction of (CpMe)3M with IMes resulted in a normal-to-abnormal NHC rearrangement.

A three-coordinate iron-silylene complex stabilized by ligand-ligand dispersion forces.

The structural and bonding properties of a three-coordinate N-heterocyclic silyene (NHSi) complex of the iron(ii) amide [Fe{N(SiMe3)2}2] are reported. Computational studies reveal that dispersion forces between the amido SiMe3 substituents and the isopropyl substituents on the NHSi ligand significantly enhance the stability of the complex, along with Fe-to-Si π-backbonding.

Molecular and electronic structures of donor-functionalized dysprosium pentadienyl complexes.

Two dysprosium complexes, [(C5H4Me)2Dy(L(1))] (3) and [(L(1))Dy(µ-Cl)3{Li(tmeda)}]2 (4), with amino-functionalized pentadienyl ligands L(1) are described. Crystallographic studies of 3 and 4 show that the pendant amino group influences the pentadienyl conformation and the ligand hapticity. Electronic structure calculations reveal that L(1) has a strong influence on the orientation of the main magnetic axis of the ground Kramers doublets in 3 and 4.

Open-shell doublet character in a hexaazatrinaphthylene trianion complex.

Three-electron reduction of hexaazatrinaphthylene (HAN) with a magnesium(I) reagent leads to [(HAN){Mg(nacnac)}3] (1), containing a [HAN](3-) ligand with a spin of S = 1/2. Ab initio calculations reveal that the [HAN](3-) ligand in 1 has a ground-state wave function with multiconfigurational properties, and can be described as a triradicaloid species with a small amount of open-shell doublet character.

Catalytic bond forming reactions promoted by amidinate, guanidinate and phosphaguanidinate compounds of magnesium.

The synthesis and catalytic properties of a series of magnesium compounds consisting of monoanionic, N,N'-chelating ligands (N∩N = amidinates, guanidinates, phosphaguanidinates) is reported. The compounds were synthesized by (i) insertion of a carbodiimide into an existing Mg-C or Mg-N bond, or (ii) protonolysis of an organomagnesium compound by a neutral pre-ligand. Structural analyses of mono- or bis-(chelate) compounds with general formula Mg(N∩N)X(L)n and Mg(N∩N)2(L)n (X = halide, aryloxide, amide; L = Et2O, THF; n = 0, 1 or 2) have been performed and the influence that the ligand substituent patterns have on the solid-state structures has been probed. Selected examples of the compounds were tested as (pre)catalysts for the polymerization of lactide, the dimerization of aldehydes and the hydroacetylenation of carbodiimides.

Hydroformylation by Pt-Sn compounds from N-heterocyclic stannylenes.

[(Me(2)Si{NAr}(2))-κ(2)N,N']Sn, reacts with PtCl(2)(L(2)) and [PtCl(µ-Cl)(L)](2) to afford products containing Pt-Sn bonds. In the absence of supporting ligands L, coordination of the stannylene and rearrangement to a structurally unique PtSn(2)N(2)Si metallacycle occurs. The hydroformylation activity of a representative Pt-Sn compound is investigated.

Synthetic and catalytic intermediates in a magnesium promoted Tishchenko reaction.

Magnesium-aryloxide and -amide compounds supported by amidinate ligands are accessible in two-steps from a suitable Grignard reagent. Both species are active for the dimerization of benzaldehyde. The slower initiation by the aryloxide was exploited in the isolation of a bis-mesitylaldehyde adduct.

Bicyclic guanidinate compounds of magnesium and their activity as pre-catalysts in the Tishchenko reaction.

A synthetic route to magnesium guanidinate compounds that avoids ligand redistribution is reported; selected derivatives are active pre-catalysts in the dimerization of aldehydes.