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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‐C5Me4tBu)(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. [ABSTRACT FROM AUTHOR]

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‐(CH2SiMe2}]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. Squarocene complexes: The potassium cyclobutadienyl [K2{η4‐C4(SiMe3)4}] reacts with MCl3(THF)3.5 (M=Y, Dy) to give the first rare‐earth cyclobutadienyl complexes, that is, the anions [M{η4‐C4(SiMe3)4}{η4‐C4(SiMe3)3‐κ‐(CH2SiMe2}]2− (2M) as their dipotassium salts. The dysprosium complex 2Dy shows single‐molecule magnet behaviour, with an anisotropy barrier of 323 cm−1 and magnetization versus field hysteresis loops up to 7 K. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] ( 1Dy Cpttt=1,2,4-tri( tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt)2Dy]+ ( 2Dy) as a salt of the non-coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [ 2Dy][B(C6F5)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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 CoII 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. [ABSTRACT FROM AUTHOR]

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)2Fe(μ-PMes)]2, which provides evidence for metal-catalyzed phosphinidene transfer. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Two dysprosium complexes, [(C5H4Me)2Dy(L1)] (3) and [(L1)Dy(μ-Cl)3{Li(tmeda)}]2 (4), with amino-functionalized pentadienyl ligands L1 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 L1 has a strong influence on the orientation of the main magnetic axis of the ground Kramers doublets in 3 and 4. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 (ItBu) (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 [(tBuIm)Co{N(SiMe3)2}2] (10). [ABSTRACT FROM AUTHOR]

Dimetallic ate complexes were synthesized from the divalent transition metal silylamide complexes {Fe[N(SiMe3)2]2}2, Cr[N(SiMe3)2]2(thf), Co[N(SiMe3)2]2(thf)2, and {Mn[N(SiHMe2)2]2}2 (thf = tetrahydrofuran) by the addition of the corresponding lithium or sodium silylamide salt. Accordingly, donor-free LiFe[N(SiMe3)2]3 and NaMn[N(SiHMe2)2]3 as well as thf-coordinated (thf)NaCr[N(SiMe3)2]3 and (thf)NaCo[N(SiMe3)2]3 were obtained. The thf-containing mixed iron(II)/lithium bis(trimethylsilyl)amide complex (thf)LiFe[N(SiMe3)2]3 was synthesized by the simple addition of thf to the donor-free complex LiFe[N(SiMe3)2]3. All of the complexes were characterized by IR spectroscopy and elemental analysis, and the effective magnetic moments in solution were determined by the Evans method. The solid-state structures of these bis(trimethylsilyl)amido-derived complexes were additionally determined by X-ray crystallography. [ABSTRACT FROM AUTHOR]

Chloride abstraction from the diamido-bismuth compound Bi(Me2Si{NAr}2)Cl (l, Ar = 2,6-i-Pr2C6H3) using MC13 (M = Al, Ga) is a facile route to cationic species. Stoichiometric reactions afford the tetrachlorometallate salts [Bi(Me2Si{NAr}2)][MCl4] (2a, M = Ah 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 [A1C14]- 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. [ABSTRACT FROM AUTHOR]

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 [(ItBu)Fe(N″)2] (4) undergoes a thermal decomposition that has not previously been observed in iron-NHC chemistry, resulting in the bis(imidazole) complex [(tBuIm)2Fe(N″)2] (7). A mechanism that involves consecutive C–H and C–N activation is proposed to account for the formation of 7. [ABSTRACT FROM AUTHOR]

Structurally characterized lithiumpentadienyls are very rare.We report the molecular structures of two lithium pentadienyls, [(pmdeta)Li{1-(R3Si)C5H6}] (3) and [(pmdeta)Li{1,5-(R3Si)2C5H5}] (4) (R3Si = Me2(NMe2)Si, pmdeta = N,N,N′,N″,N″-pentamethyldiethylenetriamine).In 3, the pentadienyl carbons adopt an η3coordination mode, whereas in 4η1coordination is found. The origins of the different coordinationmodes are discussed. [ABSTRACT FROM AUTHOR]

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

Ein intelligentes Nanosystem aus Photosensibilisator und MnO2 verbessert photodynamische Therapien, indem es den Glutathion(GSH)‐Spiegel in Krebszellen senkt. In der Zuschrift auf S. 5611 ff. zeigen W. Tan et al., dass dieses Nanosystem unter Bestrahlung intrazelluläres GSH entfernen und Singulett‐Sauerstoff erzeugen kann, um Krebszellen effizient abzutöten. Das Bild erklärt die Funktionsweise des Systems in Analogie zu einem Computerspiel. [ABSTRACT FROM AUTHOR]

Review: 47 refs. [ABSTRACT FROM AUTHOR]

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.

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., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

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., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

[(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.