21311-03-5

Upstream product

• 603-35-0 triphenylphosphine 
• 692776-43-5 fac-(η2-[60]fullerene)(η1,2-1,10-phenanthroline)tricarbonyl tungsten(0) 
• 14729-20-5 tetracarbonyl(1,10-phenanthroline)tungsten⁽⁰⁾ 

Downstream Products

• 81818-06-6 dichloro(o-phenanthroline)dinitrosyltungsten(II) 
• 82179-95-1 chloro(triphenylphosphine)dinitrosyldicarbonyltungsten(II) chloride 

Relevant academic research and scientific papers

[60]Fullerene displacement from fac-(dihapto-[60]fullerene)(dihapto-1,2- bis-(1,10-phenanthroline) tricarbonyl tungsten(0)

The Lewis bases triphenyl phosphine and tricyclohexyl phosphine (L) displace [60]fullerene (C60) from fac-(η2-C 60)(η2-phen)W(CO)3 (phen=1,10- phenanthroline) to produce fac-(η2-phen)(η su

Unexpected formation of a weak metal-metal bond: Synthesis, electronic properties, and second-order NLO responses of push-pull late-early heteronuclear bimetallic complexes with W(CO)3(1,10-phenanthroline) acting as a donor ligand

In attempts to bridge the complex [W(CO)3(phen)(pyz)] (phen = 1,10-phenanthroline; pyz = pyrazine) to acceptor centers, either soft centers such as cis-M(CO)2CL (M = Rh(I), Ir(I)) and fac-M(CO)3Cl2 (M = Ru(II), Os(II)) or hard centers such as BF3, the pyrazine ligand is lost, while the fragment W(CO)3(phen) behaves as a σ-donor base with the unexpected formation of heteronuclear early-late bimetallic compounds with a weak metal-metal bond, as confirmed by the easy substitution of W(CO)3(phen) by soft ligands (PPh3, CO, pyridine). The X-ray structures of [(CO)3(phen)W-cis-Ir(CO)2Cl] and [(CO)3(phen)W-fac-Os(CO)3Cl2] confirm a single metal-metal bond with an halogen bridging asymmetrically the two metallic moieties and with the tungsten atom achieving a distorted (6 + 1) octahedral coordination. All the heteronuclear bimetallic complexes investigated show in their electronic spectra a new solvatochromic absorption band at around 385-450 nm in addition to the MLCT (W→π*phen) absorption band typical of [W(CO)3(phen)L] complexes (L = CO, pyz, CH3CN) and an increased, in comparison to [W(CO)4(phen)], negative nonlinear (NLO) second-order emission working with the EFISH technique with an incident wavelength of 1.907 μm. The increase is due to an additional negative contribution of the new absorption band at around 385-450 nm, as shown by a solvatochromic investigation.

Systematic Tuning of the Photosubstitution Mechanism of M(CO)4(1,10-phenanthroline) by Variation of the Metal, Entering Nucleophile, Excitation Wavelength, and Pressure

The photosubstitution reactions of M(CO)4(phen) (M = Cr, Mo, W; phen = 1,10-phenanthroline) with PR3 (R = Me, Bun, Ph) to form M(CO)3(PR3(phen) were studied as a function of excitation wavelength, entering nucleophile concentration, and pressure. Ligand field photolysis in general results in a dissociative substitution mechanism. whereas charge-transfer photolysis can, depending on the nature of M and PR3, proceed according to an associative mechanism. The chemical and physical variables studied result in a systematic tuning of the photosubstitution mechanism. Nucleophile concentration, excitation wavelength, and pressure dependencies reveal unique mechanistic information. The results are discussed in reference to available literature data, and a complete mechanistic analysis is presented.

Photosubstitution reactions of M(CO)4(1,10-phenanthroline) (M = Mo, W). Influence of entering ligand, irradiation wavelength, and pressure

The influence of the entering nucleophile, irradiation wavelength, and pressure on the quantum yield for the photosubstitution of M(CO)4phen (M = Mo, W) to produce M(CO)3-(L)phen (L = PMe3, PPh3) was investigated in toluene at 298 K. From the pressure dependence of the quantum yield apparent volumes of activation could be determined as a function of irradiation wavelength. These could be analyzed in terms of contributions arising from dissociative ligand field excitation and associative metal-to-ligand charge transfer excitation. The influence of steric hindrance on the entering ligand (PPh3 > PEt3 > PMe3) controls the contribution of the associative charge-transfer photosubstitution reaction. An overall mechanistic picture is presented and discussed in reference to available literature data.

Emission and photochemistry of M(CO)4(diimine) (M = Cr, Mo, W) complexes in room-temperature solution

Electronic absorption, emission, and photochemical data are reported for a series of M(CO)4L complexes, where M = Cr, Mo, or W and L = 2,2′-bipyridine, 1,10-phenanthroline, or a derivative diimine ligand. Low-energy ligand field (LF) and intense metal-to-ligand charge-transfer (MLCT) transitions are observed in the electronic absorption spectra. The energy positions of the MLCT transitions are extremely sensitive to the nature of ligand substituent and solvent medium. Each complex exhibits dual emission features at 298 K in the 500-850-nm region and two low-lying M → π*(L) transitions are implicated in the radiative decay process. Quantum efficiencies for photosubstitution (φ) have been determined following excitation into the low-lying excited states. The photoreaction efficiences depend substantially on the irradiation wavelength; e.g., for W(CO)4(bpy) in benzene LF excitation at λ = 395 nm yields φ = 1.2 × 10-2, whereas MLCT excitation at λ = 514 nm yields φ = 5.4 × 10-5. Photosubstitution data indicate that a LF state is largely responsible for the photochemistry in these M(CO)4L complexes. The photoefficiencies following MLCT excitation at 514 nm are only slightly temperature-dependent, indicating that either the MLCT state is intrinsically photoactive or another excited state lies close in energy and contributes to the photochemistry. The suggestion of photoreaction from the low-lying LF triplet state (1A → 3E) is discussed. An excited-state scheme relating the photochemical and emission data is presented.