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Alternative coordination modes in palladium(II)-diimino-bispyridine complexes with an axially chiral biphenyl backbone

Alternative coordination modes in palladium(II)-diimino-bispyridine complexes with an axially chiral biphenyl backbone

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KETTUNEN, Mika, Christoph VEDDER, Hans-Herbert BRINTZINGER, Ilpo MUTIKAINEN, Markku LESKELÄ, Timo REPO, 2005. Alternative coordination modes in palladium(II)-diimino-bispyridine complexes with an axially chiral biphenyl backbone. In: European Journal of Inorganic Chemistry. 2005(6), pp. 1081-1089. ISSN 1434-1948. eISSN 1099-0682. Available under: doi: 10.1002/ejic.200400913

@article{Kettunen2005Alter-23695, title={Alternative coordination modes in palladium(II)-diimino-bispyridine complexes with an axially chiral biphenyl backbone}, year={2005}, doi={10.1002/ejic.200400913}, number={6}, volume={2005}, issn={1434-1948}, journal={European Journal of Inorganic Chemistry}, pages={1081--1089}, author={Kettunen, Mika and Vedder, Christoph and Brintzinger, Hans-Herbert and Mutikainen, Ilpo and Leskelä, Markku and Repo, Timo} }

European Journal of Inorganic Chemistry ; (2005), 6. - S. 1081-1089 Repo, Timo Alternative coordination modes in palladium(II)-diimino-bispyridine complexes with an axially chiral biphenyl backbone Mutikainen, Ilpo Brintzinger, Hans-Herbert terms-of-use Vedder, Christoph Leskelä, Markku Repo, Timo Brintzinger, Hans-Herbert 2013-07-24T19:11:50Z 2005 Mutikainen, Ilpo 2013-07-24T19:11:50Z The chiral biphenyl-bridged diimino-bispyridine ligandsN,N′-(6,6′-dimethylbiphenyl-2,2′-diyl)bis(2-pyridylmethyl)-diimine(1)and N,N′-(6,6′-dimethylbiphenyl-2,2′-diyl)bis[(6-methyl-2-pyridyl)methyl]diimine (2) react with Pd(COD)Cl<sub>2</sub> to give, depending on the reaction conditions, either mono- or binuclear PdCl<sub>2</sub> complexes. In the binuclear complex 1-(PdCl<sub>2</sub>)<sub>2</sub>, the Pd nuclei are held at a distance of 3.37 Å by the ligand backbone. N,N′-(6,6′-dimethylbiphenyl-2,2′-diyl)bis[(5-methyl-2-furyl)methyl]diimine (3), with furyl instead of pyridyl rings, gives mononuclear, C<sub>2</sub>-symmetric complexes only. Reactions of [Pd(NCCH<sub>3</sub>)<sub>4</sub>]<sup>2+ </sup>(BF<sub>4</sub><sup>–</sup>)<sub>2</sub> with ligand 1 or 3 give the C<sub>2</sub>-symmetric cations [1-Pd]<sup>2+</sup>or [3-Pd(NCCH<sub>3</sub>)<sub>2</sub>]<sup>2+</sup> respectively, as their BF<sub>4</sub><sup>–</sup> salts. Solid-state structures of the chloride complexes 1-PdCl<sub>2</sub>, 1-(PdCl<sub>2</sub>)<sub>2</sub> and 3-PdCl<sub>2</sub>, and of the complex cations [1-Pd]<sup>2+</sup> and [3-Pd(NCCCH<sub>3</sub>)2]<sup>2+</sup> with tetradentate and bidentate ligand coordination, respectively, all show square-planar coordination, with some distortion toward tedrahedral geometry due to the twisted biaryl-backbone. Preliminary observations on norbornene polymerization with the catalysts 1-PdCl<sub>2</sub>/MAO, 2-PdCl<sub>2</sub>/MAO and [(3-Pd(NCCH<sub>3</sub>)<sub>2</sub>]<sup>2+</sup> suggest that a certain degree of stereoregularity of the polymers is induced by these chiral catalysts. Vedder, Christoph Kettunen, Mika eng Kettunen, Mika Leskelä, Markku

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