Synthesis, Structure, and Density Functional Theory Analysis of a Scandium Dinitrogen Complex, [(C5Me4H)2Sc]2(μ-η2:η2-N2)

Demir, Selvan; Lorenz, Sara E.; Fang, Ming; Furche, Filipp; Meyer, Gerd; Ziller, Joseph W.; Evans, William J.

doi:10.1021/ja102681w

Cited by 60 publications

(60 citation statements)

References 63 publications

(126 reference statements)

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“…, as the precursor (Demir et al, 2010). Similarly, in our chemistry, initial attempts using [(NN TBS )Sc(-Cl)]2 and potassium graphite (KC8) in common organic solvents such as hexanes, toluene, diethyl ether (Et2O), tetrahydrofuran (THF) did not result in any products that could be identified.…”

Section: (Nn Tbs )Mi(thf) 2 (M = Sc Y La and Lu) As Precursors Formentioning

confidence: 66%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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Section: (Nn Tbs )Mi(thf) 2 (M = Sc Y La and Lu) As Precursors Formentioning

confidence: 66%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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“…The dilanthanide precursor complexes (Cp Me4H 2 Ln(THF)) 2 (µ-N 2 ) (Ln = Gd ( 3-Gd ), Tb ( 3-Tb ), Dy ( 3-Dy )) are readily obtained via treatment of Cp Me4H 2 Ln(BPh 4 ) with KC 8 , which prompts the reduction of dinitrogen 29, 30 . Subsequent syntheses of compounds of type 1-Ln employ KC 8 in the presence of 2.2.2-cryptand in THF to reduce the N 2 2− -bridged molecules of 3-Ln (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Synthesis details for the precursor complexes Cp Me4H 2 Ln(η 3 -C 3 H 5 ) and Cp Me4H 2 Ln(BPh 4 ), (Supplementary Figs. 62–67), where Ln = Gd, Tb, Dy, are described in the Supplementary Methods, and their preparation followed closely the route used for Cp Me4H 2 Lu(BPh 4 ) or Cp Me4H 2 Sc(BPh 4 ) 29, 30 . Preparation of the complexes Cp Me4H 2 Ln(µ-Cl 2 )K(THF) x and (Cp Me4H 2 Ln(THF))(µ-N 2 ), 3-Ln , (Supplementary Figs.…”

Section: Methodsmentioning

confidence: 99%

Giant coercivity and high magnetic blocking temperatures for N2 3− radical-bridged dilanthanide complexes upon ligand dissociation

et al. 2017

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Increasing the operating temperatures of single-molecule magnets—molecules that can retain magnetic polarization in the absence of an applied field—has potential implications toward information storage and computing, and may also inform the development of new bulk magnets. Progress toward these goals relies upon the development of synthetic chemistry enabling enhancement of the thermal barrier to reversal of the magnetic moment, while suppressing alternative relaxation processes. Herein, we show that pairing the axial magnetic anisotropy enforced by tetramethylcyclopentadienyl (CpMe4H) capping ligands with strong magnetic exchange coupling provided by an N2 3− radical bridging ligand results in a series of dilanthanide complexes exhibiting exceptionally large magnetic hysteresis loops that persist to high temperatures. Significantly, reducing the coordination number of the metal centers appears to increase axial magnetic anisotropy, giving rise to larger magnetic relaxation barriers and 100-s magnetic blocking temperatures of up to 20 K, as observed for the complex [K(crypt-222)][(CpMe4H 2Tb)2(μ−)].

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“…Also the d 10 ions Ag I and Cu I seem to have no special preference between  1 and  2 coordination. The MO and structural analysis presented here allows us to conclude that the  1 coordination of arenes is truly a -type coordination, at difference with the -type  1 coordination of Cp.…”

Section: Discussionmentioning

confidence: 95%

“…9 In some instances an aryl group of a weakly coordinating BAr 4 -counterion can also be found coordinated with a low hapticity to Sc III , Zr IV or Cu I . [10][11][12] Buchwald and coworkers have observed that the distal arene ring of coordinated biaryl phosphines often acts as an additional donor to palladium centers in an  1 or  2 mode, sometimes accompanied by dearomatization of that ring. 13 Similar  1 interactions have been found with Au I , 14 Rh I , 15 V V , 16 and Pd 0 centers.…”

Section: Introductionmentioning

confidence: 99%

Electronic and Structural Effects of Low-Hapticity Coordination of Arene Rings to Transition Metals

2014

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A DFT computational study and a structural analysis of the coordination of arenes to transition metals in low hapticity ( 1 and  2 ) modes have been developed, including a pseudosymmetry analysis of the molecular orbitals and the introduction of a hapticity map that makes evident the different degrees of intermediate hapticities.Calculations on [Pt II L 3 (C 6 H 6 )] model complexes reveal a preference for the  2 mode, while the  1 coordination is found to be a low energy transition state for a haptotropic shift. The attachment of the arene to a side group that is coordinated to the metal introduces geometrical constraints which result in hapticities intermediate between one and two. Comparison of the  1 arene complexes with benzonium cations shows that in the former case the bonding to the metal involves essentially the  system of the arene, affecting only slightly the delocalized nature of the carbon-carbon bonds. This behavior is in sharp contrast with the frequently found  1 coordination of Cp that involves  bonding and full dearomatization of the ring.2

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Synthesis, Structure, and Density Functional Theory Analysis of a Scandium Dinitrogen Complex, [(C₅Me₄H)₂Sc]₂(μ-η²:η²-N₂)

Cited by 60 publications

References 63 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Giant coercivity and high magnetic blocking temperatures for N2 3− radical-bridged dilanthanide complexes upon ligand dissociation

Electronic and Structural Effects of Low-Hapticity Coordination of Arene Rings to Transition Metals

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