Dataset Information

Grubbs and Hoveyda-Type Ruthenium Complexes Bearing a Cyclic Bent-Allene.

ABSTRACT: Stable cyclic bent-allene 1 displaces the chelating ether linkage of the Hoveyda-Grubbs-type ruthenium complex 2 bearing triphenylphosphine. The resulting complex 3 features an unusual cis-arrangement of the phosphine and the cyclic bent-allene, while retaining a distorted square pyramidal geometry around the ruthenium center. Monitoring by (31)P NMR spectroscopy the reaction of cyclic bent-allene 1 with the indenylidene bis(triphenylphosphine)ruthenium dichloride complex 4 allowed for the observation of dissociated triphenylphosphine, and the formation of a ruthenium complex featuring 1 and triphenylphosphine in the desired trans-configuration. However, continued reaction times saw the disappearance of this complex, and after workup complex 5 featuring a cis-arrangement was isolated.

SUBMITTER: Dehope A

PROVIDER: S-EPMC3134370 | biostudies-literature | 2011 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Grubbs and Hoveyda-Type Ruthenium Complexes Bearing a Cyclic Bent-Allene.

Dehope Alan A Donnadieu Bruno B Bertrand Guy G

Journal of organometallic chemistry 20110801 17

Stable cyclic bent-allene 1 displaces the chelating ether linkage of the Hoveyda-Grubbs-type ruthenium complex 2 bearing triphenylphosphine. The resulting complex 3 features an unusual cis-arrangement of the phosphine and the cyclic bent-allene, while retaining a distorted square pyramidal geometry around the ruthenium center. Monitoring by (31)P NMR spectroscopy the reaction of cyclic bent-allene 1 with the indenylidene bis(triphenylphosphine)ruthenium dichloride complex 4 allowed for the obser ...[more]

PMID: 21765542

Similar Datasets

Project description:Immobilization of the 2nd generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [( 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 Si-O-Si 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 )( 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 11111111111111111 11111111111111111 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 00000000000000000 Si-O-)2Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, 1H and 13C solid state NMR, DNP-SENS, EF-TEM…). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al···Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (dpore = 6 nm) or KCC-1 (dpore = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

Dataset Information

Grubbs and Hoveyda-Type Ruthenium Complexes Bearing a Cyclic Bent-Allene.

Publications

Grubbs and Hoveyda-Type Ruthenium Complexes Bearing a Cyclic Bent-Allene.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure