Bespoke Photoreductants: Tungsten Arylisocyanides

Sattler, Wesley; Henling, Lawrence M.; Winkler, Jay R.

doi:10.1021/ja510973h

Cited by 99 publications

(145 citation statements)

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“…DFT calculations of all three complexes in THF and pentane solutions yield bonding parameters close to those previously determined crystallographically. 1,2,18 Each complex has a distorted octahedral structure in which the three Aryl−NC−W−CN−Aryl axes are nonequivalent (the three complexes differ in the mutual orientations of the aryl rings of trans-ligands, Figure 1). For W(CNdipp) 6 and W(CNdippPh OMe 2 ) 6 , the trans aryls are nearly coplanar, 3−4°torsion angle, depending on the axis.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Electronic Excited States of Tungsten(0) Arylisocyanides

Kvapilová

Sattler

et al. 2015

Inorg. Chem.

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W(CNAryl)6 complexes containing 2,6-diisopropylphenyl isocyanide (CNdipp) are powerful photoreductants with strongly emissive long-lived excited states. These properties are enhanced upon appending another aryl ring, e.g., W(CNdippPh(OMe2))6; CNdippPh(OMe2) = 4-(3,5-dimethoxyphenyl)-2,6-diisopropylphenylisocyanide (Sattler et al. J. Am. Chem. Soc. 2015, 137, 1198-1205). Electronic transitions and low-lying excited states of these complexes were investigated by time-dependent density functional theory (TDDFT); the lowest triplet state was characterized by time-resolved infrared spectroscopy (TRIR) supported by density functional theory (DFT). The intense absorption band of W(CNdipp)6 at 460 nm and that of W(CNdippPh(OMe2))6 at 500 nm originate from transitions of mixed ππ*(C≡N-C)/MLCT(W → Aryl) character, whereby W is depopulated by ca. 0.4 e(-) and the electron-density changes are predominantly localized along two equatorial molecular axes. The red shift and intensity rise on going from W(CNdipp)6 to W(CNdippPh(OMe2))6 are attributable to more extensive delocalization of the MLCT component. The complexes also exhibit absorptions in the 300-320 nm region, owing to W → C≡N MLCT transitions. Electronic absorptions in the spectrum of W(CNXy)6 (Xy = 2,6-dimethylphenyl), a complex with orthogonal aryl orientation, have similar characteristics, although shifted to higher energies. The relaxed lowest W(CNAryl)6 triplet state combines ππ* excitation of a trans pair of C≡N-C moieties with MLCT (0.21 e(-)) and ligand-to-ligand charge transfer (LLCT, 0.24-0.27 e(-)) from the other four CNAryl ligands to the axial aryl and, less, to C≡N groups; the spin density is localized along a single Aryl-N≡C-W-C≡N-Aryl axis. Delocalization of excited electron density on outer aryl rings in W(CNdippPh(OMe2))6 likely promotes photoinduced electron-transfer reactions to acceptor molecules. TRIR spectra show an intense broad bleach due to ν(C≡N), a prominent transient upshifted by 60-65 cm(-1), and a weak down-shifted feature due to antisymmetric C≡N stretch along the axis of high spin density. The TRIR spectral pattern remains unchanged on the femtosecond-nanosecond time scale, indicating that intersystem crossing and electron-density localization are ultrafast (<100 fs).

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Section: Inorganic Chemistrymentioning

confidence: 99%

Electronic Excited States of Tungsten(0) Arylisocyanides

Kvapilová

Sattler

et al. 2015

Inorg. Chem.

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“…Single known complex of the type [CuBr(CNR) n ], viz. [CuBr(CNt-Bu) 3 ], was previously obtained (24%) by the treatment of HCN with isobutene and CuBr for 15 h at 70°C [33].…”

Section: Synthesis Of [Cubr(cnr) 3 ] Complexesmentioning

confidence: 99%

“…These species represent the first example of the crystallographically characterized [CuBr(CNR) 3 In order to clarify, whether geometrical features of the studied compounds, and in particular the bent structure of fragments M-C-N, is explained by the crystal packing effects, or are specific properties of these molecules, quantum chemical calculations were performed (for computational details see Section 4.3). If these crystal packing effects are significant, the structures should change appreciably on going from the solid state to the gas phase, otherwise the geometries are expected to be preserved in the isolated form.…”

Section: Crystal and Molecular Structuresmentioning

confidence: 99%

“…In this work, firstly, we developed a high yielding procedure for the synthesis of a series of copper-isocyanide complexes [CuBr(CNR) 3 ]. Previously one representative of this family, [CuBr(CNt-Bu) 3 ], was obtained by the addition of HCN to isobutene in the presence of CuBr [33].…”

Section: Final Remarksmentioning

confidence: 99%

“…Recent examples include design of luminescent liquid-crystalline gold complexes [1,2], photosensitizers in organic and inorganic syntheses [3], and photochromic solid materials [4]. (RNC)M species were applied as catalysts for hydroarylation of alkenes [5] and alkynes [6], alkyne hydration [7], and also for proton reduction in light-driven system [8].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Tris-isocyanide copper(I) complexes: Synthetic, structural, and theoretical study

Melekhova

Novikov

Luzyanin

et al. 2015

Inorganica Chimica Acta

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Photochemical CH Bond Activation by Gold, Platinum, Tungsten, and Osmium Complexes

Liu¹,

Tan²,

Yu³

et al. 2022

Handbook of CH-Functionalization

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To meet the increasing demand for environmentally benign and sustainable chemical processes, the use of light in organic synthesis is blossoming. Over the past decades, luminescent transition metal complexes have been extensively studied as photosensitizers due to their excellent photophysical properties and flexibility in structure modification. The visible‐light photo‐catalysis has been developed rapidly, from “proof of concept” to “a useful strategy,” in a broad range of organic transformation reactions that can be used in practical organic synthesis. Compared with the extensive literatures on ruthenium and iridium complexes used in visible‐light catalysis, the summaries on gold, platinum tungsten (except polyoxotungstates), and osmium complexes catalyzed photochemical reactions are scarce. In this article, the recent developments in photochemical reactions catalyzed by gold (Au), platinum (Pt), tungsten (W), and osmium (Os) complexes, as well as the mechanistic studies and their applications in organic synthesis are summarized. The photochemical reactions discussed herein mainly refer to the ones with transition metal complexes that absorb light in the UV–visible spectral region and which serve as a photo‐redox catalyst or a photosensitizer.

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Bespoke Photoreductants: Tungsten Arylisocyanides

Cited by 99 publications

References 61 publications

Electronic Excited States of Tungsten(0) Arylisocyanides

Electronic Excited States of Tungsten(0) Arylisocyanides

Tris-isocyanide copper(I) complexes: Synthetic, structural, and theoretical study

Photochemical CH Bond Activation by Gold, Platinum, Tungsten, and Osmium Complexes

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