Molecular and Electronic Structure of Two Linear Thiophenolate-Bridged Heterotrinuclear Complexes [LFeRuFeL]2+/3+ (L = 1,4,7-Tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)

Albela, Belén; Bill, Eckhard; Brosch, Oliver; Weyhermüller, Thomas; Wieghardt, Karl

doi:10.1002/(sici)1099-0682(200001)2000:1<139::aid-ejic139>3.0.co;2-e

Cited by 12 publications

(18 citation statements)

References 12 publications

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“…This unusual behavior of 2a may be due to a metal-metal interaction via direct metal orbital-metal orbital overlapping. 20, 21 Metal exchange reactions of the central V() atom in the Rh complex 1a using 1 equivalent of NiCl 2 or CoCl 2 were attempted (Scheme 2). As shown in Fig.…”

Section: Stability and Reactivitymentioning

confidence: 99%

Synthesis, characterization and reactivity of linear-type S-bridged trinuclear complexes containing vanadium(III) ion. Crystal structures of [VIII{M(aet)3}2](ClO4)3 (M = RhIII, IrIII; aet = 2-aminoethanethiolate)†

Miyashita

Hamajima

Yamada

et al. 2001

J. Chem. Soc., Dalton Trans.

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Reactions of fac(S)-[M(aet)3 ] (M = Rh III , Ir III ; aet = 2-aminoethanethiolate) with an excess of VCl 3 gave linear-type S-bridged trinuclear complexes [V III {M(aet) 3 } 2 ] 3ϩ (M = Rh III 1, Ir III 2). The ∆Λ isomers (1a(ClO 4 ) 3 and 2a(ClO 4 ) 3 ) were selectively crystallized and their structures were determined by X-ray diffraction. Both the complex cations consist of two terminal fac(S)-[M(aet) 3 ] units and a central vanadium atom, which is situated in an octahedral environment with a V III S 6 chromophore. The Ir complex 2a was also formed by using V IV OCl 2 instead of V III Cl 3 in a redox reaction, whereas the Rh complex 1a was not formed by a similar method. The optically active isomer (ΛΛ-1b) of the Rh complex was selectively obtained by using Λ-fac(S)-[Rh(aet) 3 ], and characterized by IR, UV-VIS absorption and CD spectra. All the obtained complexes exhibit a unique strong absorption band at ca. 18 × 10 3 cm Ϫ1 . Stability and reactivity relating to V-S bond cleavage for the complexes were investigated using UV-VIS absorption spectroscopic methods. These studies show first order decomposition or metal exchange. While 2a has weaker V-S bonds than 1a (from the X-ray analyses), the former is considerably more stable in water than the latter. Cyclic voltammograms of 1a and 2a in water show only irreversible oxidation and reduction waves including V IV/III and V III/II processes. The V() ions in the S-bridged trinuclear structures exhibit a lower magnetic moment (2.59 µ B for 1a and 2.27 µ B for 2a) at room temperature than the spin-only value for a d 2 electronic configuration. † Electronic supplementary information (ESI) available: Fig. S1 Absorption spectral change of ∆Λ-[V{Rh(aet) 3 } 2 ] 3ϩ (1a) upon addition of Co(); the curves show the spectra measured at 5 min intervals. See

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Section: Stability and Reactivitymentioning

confidence: 99%

Synthesis, characterization and reactivity of linear-type S-bridged trinuclear complexes containing vanadium(III) ion. Crystal structures of [VIII{M(aet)3}2](ClO4)3 (M = RhIII, IrIII; aet = 2-aminoethanethiolate)†

Miyashita

Hamajima

Yamada

et al. 2001

J. Chem. Soc., Dalton Trans.

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“…29 Monomeric ruthenium() complexes have also been synthesised. [30][31][32] The chemistry of a wide range of organometallic compounds containing the ruthenium 1,4,7-triazacyclononane moiety have been investigated by Che and co-workers, including olefin complexes, 33 phosphines and carbonyls, 34 π-arenes and π-cyclopentadienes, 35 and alkylidenes. 36 Several of these complexes have been found to exhibit catalytic properties in a variety of systems, including the selective oxidation of alcohols and ketones.…”

Section: Introductionmentioning

confidence: 99%

Pendant arm N-monofunctionalised 1,4,7-triazacyclononane complexes of Fe(ii) and Ru(ii)

Gott

McGowan

Podesta

2002

J. Chem. Soc., Dalton Trans.

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A series of triazacyclononane and pendant arm triazacyclononane derivatives of iron() and ruthenium() have been investigated. The objective of this work was (i) to stabilise reactive Fe() dichloride fragments using N-monofunctionalised 1,4,7-triazacyclononane macrocycles and (ii) to investigate the effect of pendant group macrocycles in order to create different Ru() environments. DALTON

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“…1 H, 7 Li, and 13 C{ 1 H} NMR spectra were recorded in C6D6 at ambient temperature on a Bruker DRX-500 spectrometer, unless otherwise specified. 1 H NMR chemical shifts are given relative to C6D5H (δ 7.16) and C6D5CD2H (δ 2.09). 7 Li NMR spectra are relative to an external LiCl (3 M in D2O) standard (0.00 ppm).…”

Section: Methodsmentioning

confidence: 99%

“…The use of 1,4,7-triazacyclononane (tacn) as a ligand in coordination chemistry has been well explored over the past few decades, with numerous reports appearing recently. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Two main features make this nine-membered macrocycle a useful ligand. First, its three nitrogen atoms provide for tridentate, facial coordination to a metal center.…”

Section: Introductionmentioning

confidence: 99%

Reactions of a Triazacyclononane-Supported Tantalum−Lithium Bridging Alkylidene with Organic Substrates

Schmidt

Arnold

2002

Organometallics

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The reactivity of a range of electrophilic organic substrates with a heterobimetallic tantalum-lithium bridging alkylidene [(Me 3 SiCH 2 )(ArNd)Ta(µ-CHSiMe 3 )(µ-η 1 :η 3 -i Pr 2 -tacn)-Li, 3] is presented. Proton sources of widely varying acidity react to protonate the alkylidene ligand, leading to an interesting tantalum-lithium bridging hydride complex in the case of H 2 . The alkylidene 3 undergoes a series of insertion reactions with unsaturated substrates, such as acetonitrile, carbon monoxide, and carbon disulfide; it also reacts with an acid chloride to yield a tantalum enolate species featuring return of the i Pr 2 -tacnligand to a tridentate coordination mode. The incorporated lithium in 3 played an important role, at least structurally, in the chemistry observed.

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Molecular and Electronic Structure of Two Linear Thiophenolate-Bridged Heterotrinuclear Complexes [LFeRuFeL]2+/3+ (L = 1,4,7-Tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)

Cited by 12 publications

References 12 publications

Synthesis, characterization and reactivity of linear-type S-bridged trinuclear complexes containing vanadium(III) ion. Crystal structures of [VIII{M(aet)3}2](ClO4)3 (M = RhIII, IrIII; aet = 2-aminoethanethiolate)†

Synthesis, characterization and reactivity of linear-type S-bridged trinuclear complexes containing vanadium(III) ion. Crystal structures of [VIII{M(aet)3}2](ClO4)3 (M = RhIII, IrIII; aet = 2-aminoethanethiolate)†

Pendant arm N-monofunctionalised 1,4,7-triazacyclononane complexes of Fe(ii) and Ru(ii)

Reactions of a Triazacyclononane-Supported Tantalum−Lithium Bridging Alkylidene with Organic Substrates

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