Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Ruiz, Javier; Ceroni, Mario; Quinzani, Oscar V.; Piro, Oscar E.

doi:10.1002/1521-3757(20010105)113:1<226::aid-ange226>3.0.co;2-z

Cited by 9 publications

(3 citation statements)

References 11 publications

(9 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, the usually compact and symmetric shape of the polynuclear complexes seems to result in a significantly smaller magnetic anisotropy than that found in the isolated building blocks composed of mononuclear metal complexes.From a theoretical point of view, the development of DFT in recent years has reached the point that it allows us to calculate, with remarkable success, the exchange coupling constants in very large polynuclear systems. [13][14][15] The calculated coupling constants provide an accurate description of the magnetic behavior at the microscopic level that cannot be extracted from measurements of the magnetic susceptibility. The knowledge of such coupling constants associated with a given bridging ligand is extremely useful for the design of new molecular systems with large spin values.In contrast, the determination of the ZFS parameters for transition-metal complexes has been a problem both for experimentalists [16][17][18] and for theoreticians.…”

mentioning

confidence: 99%

“…From a theoretical point of view, the development of DFT in recent years has reached the point that it allows us to calculate, with remarkable success, the exchange coupling constants in very large polynuclear systems. [13][14][15] The calculated coupling constants provide an accurate description of the magnetic behavior at the microscopic level that cannot be extracted from measurements of the magnetic susceptibility. The knowledge of such coupling constants associated with a given bridging ligand is extremely useful for the design of new molecular systems with large spin values.…”

mentioning

confidence: 99%

See 1 more Smart Citation

How to Build Molecules with Large Magnetic Anisotropy

Cirera

Ruiz

Álvarez

et al. 2009

Chemistry A European J

171

150

View full text Add to dashboard Cite

Predicting single-molecule magnets? Magnetic anisotropy, a property that plays a key role in single-molecule magnets (SMMs), has been analyzed by using theoretical methods. Mononuclear complexes and the dependence of the magnetic anisotropy on their geometrical and electronic structure, as well as how such mononuclear complexes must be combined as building blocks to obtain polynuclear complexes with large anisotropy (see figure) are considered.The magnetic anisotropy of mononuclear transition-metal complexes has been studied by means of electronic structure calculations based on density functional theory. The variation of the zero-field splitting (ZFS) parameters has been analyzed for the following characteristic distortions: a tetragonal Jahn-Teller distortion, the Bailar twist, the Berry pseudorotation, and the planarization of tetrahedral complexes. Finally, the coupling of mononuclear building blocks in polynuclear complexes to obtain a large negative magnetic anisotropy necessary to improve their single-molecule-magnet (SMM) behavior has been studied.

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

How to Build Molecules with Large Magnetic Anisotropy

Cirera

Ruiz

Álvarez

et al. 2009

Chemistry A European J

171

150

View full text Add to dashboard Cite

show abstract

“…The procedure employed by us here for the estimation of the set of exchange-coupling constants in an extended compound with n different J ij values consists of the calculation of (n + 1) energies corresponding to different spin distributions within the unit cell. It is similar to that employed for molecular polynuclear complexes, [27,28] but is restricted to the unit cell. We can use such energies to obtain a system of n equations with n unknowns, the J ij values.…”

Section: Dft Calculationsmentioning

confidence: 99%

H‐Mediated Magnetic Interactions between Layers in a 2D Mn^II–Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations

et al. 2017

View full text Add to dashboard Cite

Abstract:We report neutron-diffraction investigations of the quasi-2D Mn II (dca) 2 (pym)(H 2 O) (pym = N 2 C 4 H 4 ) compound, where high-spin Mn II ions are bridged by dicyanamide anions, [N(CN) 2 ] -(herein abbreviated dca). Inside the layers, Mn 2+ ions are connected by single or double dca bridges. The magnetic phase diagram was established by neutron diffraction on a single crystal. In the low-field phase, the Mn II ions are antiferromagnetically ordered in the layers, with moments nearly parallel to the c axis, and the layers are antiferromagnetically coupled. The spin-flop phase corresponds to ferromagnetic coupling between the antiferromagnetic layers, in which the

show abstract

New Approach to the Chemistry of Polysulfides Using Diphosphanylmethanide Complexes of Manganese(I)

Ruiz¹,

Ceroni²,

Quinzani³

et al. 2001

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

The study of the nucleophilic degradation of S8 by the methanide complex [Mn(CO)4[(PPh2)2CH]] (2) has led to the preparation of a unique class of polysulfide derivatives of formula [(CO)4Mn[(PPh2)2C-Sn-C(PPh2)2]-Mn(CO)4]. The structures of 3 (n = 6), 4 (n = 2), and 7 (n = 1) have been determined by X-ray crystallography, whereas those polysulfides with the sulfur chains S7, S5, S4, and S3 have been detected by spectroscopic methods. The polysulfides with n > 2 lose sulfur spontaneously, a process that can be accelerated by treatment with PPh3 or Na/Hg. Complexes 3, 4, and 7 were protonated at the two methanide carbon atoms to give the cationic dinuclear derivatives [(CO)4Mn[(PPh2)2C(H)-Sn-C(H)-(PPh2)2]Mn(CO)4]2+ (8, n=6; 9, n=2; 10, n = 1). The 1H NMR spectrum of 9 suggests the existence of intramolecular C-H...S interactions, in agreement with the X-ray structural determination of this complex. By treatment of 4 and 7 with one equivalent of HBF4 it is possible to selectively protonate just one methanide carbon atom, which allows the isolation of the mixed cationic derivatives R(CO)4Mn[(PPh2)2C(H)-Sn-C(PPh2)2]Mn(CO)4]+ (11, n = 2; 6, n = 1). Additionally, heterometallic complexes containing a bridging disulfide unit, of general formula [(CO)4Mn[(PPh2)2C(AuPPh3)S-SC-(AuPPh3)(PPh2)2]Mn(CO)4]2+ (12) and [(CO)4Mn[(PPh2)2C(H)S-SC(AuPPh3)-(PPh2)2]Mn(CO)4]+ (13), were prepared by reaction of 4 and 11, respectively, with [AuCl(PPh3)] in the presence of TlPF6.

show abstract

Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Cited by 9 publications

References 11 publications

How to Build Molecules with Large Magnetic Anisotropy

How to Build Molecules with Large Magnetic Anisotropy

H‐Mediated Magnetic Interactions between Layers in a 2D Mn^II–Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations

New Approach to the Chemistry of Polysulfides Using Diphosphanylmethanide Complexes of Manganese(I)

Contact Info

Product

Resources

About

Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Cited by 9 publications

References 11 publications

How to Build Molecules with Large Magnetic Anisotropy

How to Build Molecules with Large Magnetic Anisotropy

H‐Mediated Magnetic Interactions between Layers in a 2D MnII–Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations

New Approach to the Chemistry of Polysulfides Using Diphosphanylmethanide Complexes of Manganese(I)

Contact Info

Product

Resources

About

H‐Mediated Magnetic Interactions between Layers in a 2D Mn^II–Dicyanamide Polymer: Neutron Diffraction, DFT, and Quantum Monte Carlo Calculations