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C-H activation of diphenylphosphinoaryl-derivatives with dimethyltetrakis(trimethylphosphine)iron(II) |
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| Authors: | Robert Beck Tingting Zheng Xiaoyan Li Hans-Friedrich Klein |
| Institution: | a School of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, 250100 Jinan, PR China b Eduard-Zintl-Institut für Anorganische und Physikalische Chemie der Technischen Universität, Darmstadt, Petersenstrasse 18, 64287 Darmstadt, Germany c Anorganische und Analytische Chemie, Universität Paderborn, Warburger Straße 100, D-33098 Paderborn, Germany |
| Abstract: | Fe(CH3)2(PMe3)4 reacts with 1-(diphenylphosphino)naphthalene or benzyldiphenylphosphine within 4 h at 20 °C to give the novel metallated methyl iron complexes Fe(CH3){P(C6H5)2(C10H6)}(PMe3)3 (1) and Fe(CH3){(C6H4)CH2P(C6H5)2}(PMe3)3 (3), respectively, via selective activation of the C-H bond of the pre-chelating ligands. The complexes are thermally unstable releasing metal through a reductive elimination of the aromatic backbone and leading to a C,C-coupling product that is regiospecifically methylated, namely 8-methyl(diphenylphosphino)naphthalene (2). Carbonylation (1 bar, 20 °C, 1 h) of complex 1 effects monosubstitution of a trimethylphosphine ligand trans to the metallated 8-C atom to afford Fe(CH3){P(C6H5)2(C10H6)}(CO)(PMe3)2 (4). The remaining methyl group in the parent complex 1 reacts with trimethylsilylethyne and tert-butylethyne affording the new complexes 5 and 6 bearing an alkynyl substituent trans to the diphenylphosphino anchoring group. The complexes 1 and 3-6 are diamagnetic and possess octahedral coordination geometry. All novel complexes were fully characterized by spectroscopic methods and by X-ray diffraction. |
| Keywords: | C-H Activation C C-coupling Iron P ligands |
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