Homoleptic and related aryls of transition metals

Koschmieder, Stefan U.; Wilkinson, Geoffrey

doi:10.1016/s0277-5387(00)81585-5

Cited by 47 publications

(32 citation statements)

References 163 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Structural studies are summarized in a review. 2 This paper expands on a preliminary report3 in which the synthesis and X-ray crystal structure of tris(mesityl)rhodium(rrr) were described; reactions of the latter and of the rhodium(I1) compound trans-Rh(2,4,6-Pri3C,H,),(tht), (tht = tetrahydrothiophene) are now given, together with synthesis of a benzyl complex. Although iridium analogues of none of these species have yet been made, the paramagnetic, tetrahedral tetramesityl, Ir(mes), (mes = 2,4,6-Me3C,H,), has been structurally characterized., Analytical and physical data for new compounds are given in Table 1…”

mentioning

confidence: 75%

Aryl compounds of rhodium: syntheses and X-ray crystal structures

Hay-Motherwell¹,

Koschmieder²,

Wilkinson³

et al. 1991

J. Chem. Soc., Dalton Trans.

Self Cite

View full text Add to dashboard Cite

mentioning

confidence: 75%

Aryl compounds of rhodium: syntheses and X-ray crystal structures

Hay-Motherwell¹,

Koschmieder²,

Wilkinson³

et al. 1991

J. Chem. Soc., Dalton Trans.

Self Cite

View full text Add to dashboard Cite

“…1 H and 13 C{ 1 H} NMR spectra were recorded at room temperature on Varian VNMRS 500 (500 MHz), 400MR (400 MHz), VNMRS 600 (600 MHz), or Mercury 400 (400 MHz) NMR spectrometers, unless otherwise stated. 1 H NMR data recorded in CDCl3, CD2Cl2, C6D6, and toluene-d8 is referenced to residual internal CHCl3 (𝛿 7.26), CDHCl2 (𝛿 5.32), C6D5H (𝛿 7.16), and C6D5CD2H (𝛿 2.08) solvent signals. 27 13 C{ 1 H} NMR data recorded in CDCl3 is referenced to internal CDCl3 (𝛿 77.16).…”

Section: Materials and Instrumentsmentioning

confidence: 99%

“…Spectroscopic data was consistent with previous reports. 22 1 H NMR (CDCl3, 500 MHz): δ (ppm) 2.34 (s, 12H), 2.54 (s, 6H), 7.00 (s, 4H). 1 H NMR (C6D6, 400 MHz): δ (ppm) 2.27 (s, 6H), 2.35 (s, 12H), 6.74 (s, 4H).…”

Section: Os(mesityl)4 (Os3) and Oso2(mesityl)2mentioning

confidence: 99%

“…Homoleptic transition metal(IV) tetraaryl complexes, M(aryl)4, are an underexplored class of organometallic materials with distinct electrochemical, magnetic, and optical characteristics resulting from their tetrahedral coordination geometry. 1 Their properties complement and extend beyond those of their isostructural group 14 congeners, widely utilized as primary components of advanced molecular materials such as covalent-and metal-organic frameworks, 2-5 polymers, 6 self-assembled monolayers, [7][8][9][10] and single-molecule electronic components. 11,12 We anticipate that modular, isostructural M(aryl)4 units can provide new approaches, for example, to tune the electrochemical energy storage capacity, electrocatalytic function, and electrical conductivity/conductance of such materials, among other applications.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

An improved route to osmium(IV) tetraaryl complexes

Parr¹,

Olivar

Saal

et al. 2021

Preprint

View full text Add to dashboard Cite

Investigations into the reactivity, properties, and applications of osmium(IV) tetraaryl complexes have been hampered by their low yielding syntheses from volatile and toxic OsO4 (typically ≤34%). Here we show that air-stable M(aryl)4 compounds (M = Os, Ru; aryl = 2-tolyl, 2,5-xylyl) can be prepared in improved yields (≤73%) starting from new, less hazardous (Oct4N)2[MX6] precursors (M = Os, Ru; X = Cl, Br). This approach also facilitates the preparation of Os(mesityl)4 (Os3), a complex comprising bulky 2,6-methyl substituted aryl ligands, for the first time (5% yield). We evaluate the X-ray crystal structures of Os(2,5-xylyl)4 (Os2) and Os3, employing a "tetrahedricity" metric that shows Os3 has a particularly distorted tetrahedral geometry compared to other Ru(aryl)4 and Os(aryl)4 materials. The 1H NMR spectrum of Os3 exhibits significantly broadened features at 298 K that split into distinct resonances at low temperatures, indicative of restricted rotation of the mesityl ligands around the Os-aryl 𝜎-bond. Solution cyclic voltammograms of Os(aryl)4 reveal that the potentials of their known reversible redox features can be fine-tuned by varying the number of ligand methyl substituents, and that Os3 exhibits an additional 1+/2+ redox event not previously observed in this class of compounds. This work aims to help advance the potential application of these relatively underexplored organometallic complexes in established and emerging areas of molecular materials science, such as extended molecular frameworks and self-assembled monolayers, where analogous tetraphenylmethane and silane species (M = C, Si) have been frequently targeted.

show abstract

“…A review covering several of the earlier sections in this chapter, but with special reference to a-aryl complexes, is available. 1 …”

Section: Introductionmentioning

confidence: 99%