Photochemical reactions of Group 6 metal carbonyls with alkenes

Szymańska-Buzar, Teresa

doi:10.1016/j.ccr.2005.12.002

Cited by 25 publications

(24 citation statements)

References 101 publications

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“…The corresponding (η 2 -olefin) 3 -W(CO) 3 complexes of simple monoolefins have been detected [33] in photoprocesses of W(CO) 4 (η 2 -alkene) 2 in alkane solution at low temperatures but are reported to be unstable under ambient conditions. [34] However, the analogous mer-(η 2 -ethene)(η 4 -norbornadiene)W(CO) 3 is much more stable, [35] since two of the three double bonds complexed to the tungsten atom arise from the chelating diolefin norbornadiene.…”

Section: Resultsmentioning

confidence: 98%

Inhibition of Alkyne Cyclotrimerization to Arenes on a Metal Site by Four‐Electron Donation through Simultaneous Sigma and Pi Bonding: The Tris(alkyne)Tungsten Carbonyls

Peng

Xie

et al. 2009

Eur J Inorg Chem

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Reactions of fac‐(CH3CN)3W(CO)3 with the alkynes RC≡CR are known experimentally to give the very stable (RC≡CR)3WL (L = CO or CH3CN) complexes without the complexed alkyne ligands on the tungsten site undergoing cyclotrimerization to the corresponding benzene derivatives C6R6. In order to evaluate the thermodynamics of these systems, the structures and energetics of the tris(alkyne)tungsten carbonyls (RC≡CR)3W(CO)n and the corresponding arenetungsten carbonyls (η6‐C6R6)W(CO)n (R = CH3, CF3; n = 3, 2, 1, 0) have been optimized using density functional theory. The cyclotrimerizations of the alkyne ligands in (RC≡CR)3W(CO)n (n = 3, 2) to a benzene ligand in (η6‐C6R6)W(CO)n are predicted to be very exothermic. However, the corresponding cyclotrimerizations of the alkyne ligands in (RC≡CR)3W(CO) and (RC≡CR)3W to a benzene ligand in (η6‐C6R6)W(CO) and (η6‐C6R6)W, respectively, are predicted to range from nearly thermoneutral (R = CH3) to highly endothermic (R = CF3). This can be related to the bonding mode of the alkyne ligands to the tungsten atom. Alkyne ligands bonded to tungsten as four‐electron donors (with one σ bond and one π bond) are resistant to cyclotrimerization reactions. However, alkyne ligands bonded to tungsten as two‐electron donors through only σ bonding of the C≡C triple bond are reactive towards cyclotrimerization reactions. The CF3 derivatives are found to be less reactive towards cyclotrimerization than the CH3 derivatives. The inhibition of alkyne cyclotrimerization on a metal site by bonding as a four‐electron donor through both σ and π bonding can be related to the fact that known alkyne cyclotrimerization catalysts are generally based on late transition metals of groups 8, 9, and 10, rather than early transition metals such as tungsten.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Resultsmentioning

confidence: 98%

Inhibition of Alkyne Cyclotrimerization to Arenes on a Metal Site by Four‐Electron Donation through Simultaneous Sigma and Pi Bonding: The Tris(alkyne)Tungsten Carbonyls

Peng

Xie

et al. 2009

Eur J Inorg Chem

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“…Also, the 1 H NMR spectrum exhibit doublet signal at 8.3 ppm due to (Ar-CH=CH-, J = 12.3 Hz), as well as multiplets in the range 6.90-7.8 ppm due to the phenyl protons. [29][30][31][32][33] . These 16-electron containing M(CO) 5 fragments react avidly with either the ligand alone to give metal derivative (as with group 8 products) 34 or with the ligand and oxygen to give oxocomplexes [as with group 6 products).…”

Section: Resultsmentioning

confidence: 99%

Reactions of 2'-hydroxy methoxylated chalcone with group 6 and 8 metal carbonyl complexes under sunlight irradiation: Synthesis, characterization, spectroscopic investigation and biological activities

2010

Egyptian Journal of Pure and Applied Science

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Sunlight irradiation of the reactions of either [M(CO) 6 ], M=Cr, Mo and W or [M 3 (CO) 12 ], M = Ru or Os with 1-(2'-Hydroxyphenyl)-3-(3``,4``dimethoxyphenyl)-2-propen-1-one, 1, in benzene were investigated. Three dinuclear complexes with molecular formulas [Cr 2 O 2 (ChO) 2 ], 2, [Mo 2 O 4 (ChO) 2 ], 3, [W 2 O 4 (ChO) 2 ], 4, were isolated from the reactions with 1. The corresponding reactions of 1 with group 8 cluster complexes produced the complexes, [Ru 3 (CO) 10 (ChO)], 5, and [Os 3 (CO) 10 (ChOH)], 6.All complexes were characterised by elemental analysis, infrared, 1 H-NMR, ( 13 C-NMR for 1), mass and ESR spectroscopy. The UV-vis spectra of the complexes showed visible bands due to either ligand-to-metal or metal-to-ligand charge transfer. Thermal properties of the complexes were investigated by TG thermogravimetric technique. The synthesized 1 (ligand) and its complexes were screened for their antibacterial activity against two gram positive bacteria, two gram negative bacteria and fungi candida albicans. The activity was compared with Amikacin as standard.

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“…CO taşıyıcı ve salıcı moleküller söz konusu olduğunda akla ilk gelen aday metal karbonil kompleksleridir [23]. Bu komplekslerin belirli dalga boylarında UV-Görünür Bölge ışığına hassasiyetleri bilindiğinden [24] [28][29][30][31].…”

Section: Introductionunclassified

“…Aslında CO, hemoglobinin degradasyon sürecinde yan ürün olarak sentezlendiği, dokuda her zaman bir miktar bulunduğu [3] CO taşıyıcı ve salıcı moleküller söz konusu olduğunda akla ilk gelen aday metal karbonil kompleksleridir [23]. Bu komplekslerin belirli dalga boylarında UV-Görünür Bölge ışığına hassasiyetleri bilindiğinden [24] fotoaktivasyon yolunu kullanmak için önemli aday moleküllerdir. PhotoCORMs moleküllerin gerekli olduğu dokuya ulaştığında derişim ve zaman kontrollü olarak CO salınım yapabilme gibi avantajlarının yanında kullanılan muhtemel düşük dalga boylu ışının dokuda meydana getirmesi muhtemel zararlar gibi dezavantajları da vardır.…”

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DFT/TDDFT Analysis of [Mn(CO)3(bpy)L]X Type Complexes with Benzimidazole Derivative Ligands

Üstün¹

2017

Cumhuriyet Science Journal

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Karbon monoksit molekülünün doku için sadece toksik değil tedavi edici de olduğunun anlaşılmasından sonra, güvenli ve kontrollü karbon monoksit taşıma ajanı olarak metal karbonil komplekslerinin kullanılmaya başlanması, bu tür komplekslere olan ilginin son yıllarda artmasına neden olmuştur. Bu nedenle pek çok yeni kompleks sentezlenip karakterize edilmiş ve CO-salınım aktiviteleri incelenmiştir. Hedef dokuya en uygun COsalıcı molekülü bulabilmek için pek çok molekülün sentezi gerekir ki bu durum zaman ve ekonomik kısıtlamalardan dolayı tercih edilen bir yol değildir. Fakat sentezi planlanan bir molekülün DFT/TDDFT hesaplarının yapılması, moleküllerin bir kısım özelliklerinin öngörülmesini sağlayabilir. CO-salınımı açısından bu öngörünün oluşabilmesi için sentezi yapılarak CO-salınımı incelenmiş fazla sayıda molekülün deneysel sonuçları ile teorik/hesaplamalı sonuçlarının karşılaştırılması gerekir. Bu çalışmanın amacı, BP86 ve B3LYP fonksiyonelleri ile kararlılıklarının karşılaştırılması için [Mn(CO) 3 (bpy)L]X (

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Photochemical reactions of Group 6 metal carbonyls with alkenes

Cited by 25 publications

References 101 publications

Inhibition of Alkyne Cyclotrimerization to Arenes on a Metal Site by Four‐Electron Donation through Simultaneous Sigma and Pi Bonding: The Tris(alkyne)Tungsten Carbonyls

Inhibition of Alkyne Cyclotrimerization to Arenes on a Metal Site by Four‐Electron Donation through Simultaneous Sigma and Pi Bonding: The Tris(alkyne)Tungsten Carbonyls

Reactions of 2'-hydroxy methoxylated chalcone with group 6 and 8 metal carbonyl complexes under sunlight irradiation: Synthesis, characterization, spectroscopic investigation and biological activities

DFT/TDDFT Analysis of [Mn(CO)3(bpy)L]X Type Complexes with Benzimidazole Derivative Ligands

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