Ruthenium-Catalyzed Dimerization of Terminal Alkynes Initiated by a Neutral Vinylidene Complex

Author:

Slugovc Christian1,Mereiter Kurt1,Zobetz Erich1,Schmid Roland1,Kirchner Karl1

Affiliation:

1. Institute of Inorganic Chemistry and Institute of Mineralogy, Crystallography, and Structural Chemistry, Technical University of Vienna, Getreidemarkt 9, A-1060 Vienna, Austria

Publisher

American Chemical Society (ACS)

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry

Reference19 articles.

1. Ruthenium Tris(pyrazolyl)borate Complexes. 1. Synthesis and Reactivity of Ru(HB(pz)3)(COD)X (X = Cl, Br) and Ru(HB(pz)3)(L2)Cl (L = Nitrogen and Phosphorus Donor Ligands)

2. Ruthenatetraboranes: synthesis of [Ru(B3H8)(PPh3)}HB(pz)3}] and crystal structure of [RuCl(PPh3)2{HB(pz)3}] (pz = pyrazol-1-yl)

3. Procedure and data for4: A solution of1(600 mg, 0.686 mmol) in dry THF (5 mL) was treated with HC⋮CPh (300 μL, excess) and stirred for 36 h at room temperature. After removal of the solvent the residue was dissolved in 0.5 mL of CH2Cl2and the product was precipitated with diethyl ether. Yield:  423 mg (92%). Anal. Calcd for C35H31BClN6PRu:  C, 58.88; H, 4.38; N, 11.77. Found:  C, 58.99; H, 4.54; N, 11.47.1H NMR (δ, CDCl3, 20 °C):  7.94 (d, 1H,J= 2.1 Hz), 7.73 (d, 1H,J= 2.5 Hz), 7.70 (d, 1H,J= 2.5 Hz), 7.64−7.56 (m, 7H), 7.44−7.37 (m, 3H), 7.31−7.24 (m, 8H), 7.18−7.04 (m, 3H), 6.80 (d, 1H,J= 2.1 Hz), 6.16 (dd, 1H,J= 2.1 Hz,J= 1.8 Hz), 6.01 (d, 1H,J= 2.1 Hz), 5.98 (dd, 1H,J= 2.5 Hz,J= 2.5 Hz), 5.82 (dd, 1H,J= 2.1 Hz,J= 2.1 Hz), 4.98 (d, 1H,4JPH= 3.9 Hz).13C{1H} NMR (δ, CDCl3, 20 °C):  368.9 (d, 1C, Cα,2JCP= 18.8 Hz), 145.5, 144.1, 144.0 (d,3JCP= 1.7 Hz), 137.1, 135.3 (d,2JCP= 10.2 Hz), 134.8 (d,3JCP= 2.5 Hz), 132.6 (d,1JCP= 44.9 Hz), 130.9 (d, 1C, Ph,3JCP= 1.7 Hz), 130.5 (d, 1C, Ph,4JCP= 2.5 Hz), 129.3 (2C Ph), 128.5 (d,3JCP= 10.2 Hz), 126.6 (2C, Ph), 125.6 (1C, Ph), 112.7 (d, 1C, Cβ,3JCP= 1.7 Hz), 106.5 (d,4JCP= 2.5 Hz), 106.4, 106.2.31P{1H} NMR (δ, CDCl3, 20 °C):  37.5. IR (diffuse reflectance, cm-1):  2483 (m, B−H), 1647 (s, CC).

4. Organometallic chemistry of vinylidene and related unsaturated carbenes

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