HINDERED LIGAND MOVEMENTS IN TRANSITION-METAL COMPLEXES DECARBONYL (ETA-4-DIENE) TUNGSTEN(0)

Date

1992-08-04

Author

Özkar, Saim
KREITER, CG

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

16
views

0
downloads

1,2-Bis(dimethylphosphino)ethane-dicarbonyl-eta-4-diene-tungsten(0) complexes (diene = 1,3-butadiene (1), E-1,3-pentadiene (2), E,E-2,4-hexadiene (3) and E-2-methyl-1,3-pentadiene (4)) were synthesized by UV irradiation of 1,2-bis(dimethylphosphino)ethane-tetracarbonyltungsten(0) and the corresponding dienes in toluene. The constitutions of these complexes were determined by IR and NMR spectroscopy (H-1, C-13, P-31). The spectral data indicate pseudo-octahedral structures for the complexes. When the dienes are assigned to the positions b and c of the coordination octahedron, the 1,2-bis(dimethylphosphino)ethane occupies a and d (e), the two carbonyls e (d) and f positions. 1 and 3 show temperature-dependent NMR signals according to hindered ligand movements with barriers of activation of 50 and 59 kJ mol-1. In contrast, as a consequence of very different isomer populations, no ligand movement is observed for 2 and 4 up to 353 K.

Subject Keywords

Motions, Derivatives, Dynamic behavior, Nuclear magnetic-resonance

URI

https://hdl.handle.net/11511/41392

Journal

JOURNAL OF ORGANOMETALLIC CHEMISTRY

DOI

https://doi.org/10.1016/0022-328x(92)83355-l

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Pyramidalized double bonds containing endoperoxide linkages: Photooxygenation of dimethyl cis-3,8-dihydroheptalene-3,8-dicarboxylate Saracoglu, N; Menzek, A; Sayan, S; Salzner, U; Balcı, Metin (1999-09-03) Diels-Alder cyclo;addition utilizing singlet oxygen as the dienophile with dimethyl cis-3,8-dihydraheptalene-3,8-dicarboxylate (5) has been investigated, and monoaddition product 7 has been isolated. The addition of a second singlet oxygen to the cycloheptatriene unit in 7 gave syn-bis(norcaradiene) bis(endoperoxide) 4. H-1 NMR spectral studies and theoretical calculations indicate the increased pyramidalization in syn-4 compared with carbon analogue. The increased pyramidalization results from hyperconjuga...
Effect of substituents in sulfoxides on the enhancement of thermoelectric properties of PEDOT:PSS: experimental and modelling evidence Zhu, Qiang; Yıldırım, Erol; Wang, Xizu; Kyaw, Aung Ko Ko; Tang, Tao; Soo, Xiang Yun Debbie; Wong, Zicong Marvin; Wu, Gang; Yang, Shuo-Wang; Xu, Jianwei (2020-06-01) Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), being the most popular conductive polymer, has been doped with various additives with the aim of improving its thermoelectric performance. Among all additives, dimethyl sulfoxide (DMSO) has been widely used for various treatments. In this work, we designed and synthesized a series of aliphatic- and aromatic-substituted sulfoxides as dopants to improve the thermoelectric properties of PEDOT:PSS. It was found that the substituents in the sul...
Insertion of Fischer Carbene Complexes into the Carbon-Carbon Bond of 1,2-Diphenylcyclopropenone: Formation of Cyclobutenones and o- and p-Methoxyphenol Derivatives Zora, Metin (American Chemical Society (ACS), 1994-08-01) Thereactionbetween1,2-diphenylcyclopro-penoneandFischercarbenecomplexeshasbeeninves-tigated.Thereactionproducedamixtureofdipheny-lacetyleneandcyclobutenones.Whena,ß-unsaturatedcarbenecomplexeswereemployed,benzannulationprod-uctsanddiphenylacetylenewereproduced.Amecha-nisminvolvingmetallacyclobutenoneformation,followedbyeithercarbeneinsertionandreductiveeliminationorfragmentationhasbeenproposed.Recently,wereportedthatcarbon—carbonbondin-sertionisthemajorreactionpathwaywhenFischercarbenecomplexesreactwith1,2-...
A theoretical study on camptothecin-AM1 treatment Türker, Burhan Lemi (2001-08-13) Camptothecin (irinotecan), a new cytotoxic agent having antitumor activity and especially used in the treatment of advanced colorectal cancers is considered for AM1-RBF type semiempirical quantum chemical treatment together with some analogs of camptothecin. The structural properties and energetics of these molecules have been compared. The structures arising from monoprotonation of camptothecin at various sites are analyzed from thermodynamic point of view.
Crosslinking of Trimethylene Carbonate and D,L-Lactide (Co-) Polymers by Gamma Irradiation in the Presence of Pentaerythritol Triacrylate Bat, Erhan; Feijen, Jan; Grijpma, Dirk W. (Wiley, 2011-07-07) High-molecular-weight (co) polymers of trimethylene carbonate and D, L-lactide are efficiently crosslinked using PETA during gamma irradiation. Form-stable networks with gel contents of 86 +/- 5 to 96 +/- 1 are obtained from non-crystalline (co) polymers. Glass transition temperatures and elastic moduli of the networks can be varied by adjusting the copolymer composition. The PETA-containing (co) polymer networks are not cytotoxic. Upon incubation in macrophage cultures for 14 d, all (co) polymer films and ...

Citation Formats

S. Özkar and C. KREITER, “HINDERED LIGAND MOVEMENTS IN TRANSITION-METAL COMPLEXES DECARBONYL (ETA-4-DIENE) TUNGSTEN(0),” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 79–87, 1992, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/41392.