Ruthenium Carbonyl Complexes Bearing Bis(pyrazol-1-yl)carboxylato Ligands

The syntheses of the two dicarbonyl complexes [Ru­(bdmpza)­Cl­(CO)₂] (<b>3</b>) and [Ru­(2,2-bdmpzp)­Cl­(CO)₂] (<b>4</b>), bearing a bis­(3,5-dimethylpyrazol-1-yl)­acetato (bdmpza) or a 2,2-bis­(3,5-dimethylpyrazol-1-yl)­propionato (2,2-bdmpzp) scorpionate ligand, are described. Both complexes are obtained by reacting the polymer [RuCl₂(CO)₂]_<i>n</i> with either K­[bdmpza] or K­[2,2-bdmpzp]. Reaction of the acid Hbdmpza with [Ru₃(CO)₁₂] results in the formation of two structural isomers of a hydrido complex, [Ru­(bdmpza)­H­(CO)₂] (<b>5a</b>,<b>b</b>). Under aerobic conditions conversion of [Ru­(bdmpza)­H­(CO)₂] (<b>5a</b>,<b>b</b>) to form the Ru­(I) dimer [Ru­(bdmpza)­(CO)­(μ-CO)]₂ (<b>6</b>) seems to be hindered in comparison to the case for the η⁵-C₅H₅ (Cp) analogues. Dimer <b>6</b> is obtained via a reaction of Hbdmpza with <i>catena</i>-[Ru­(OAc)­(CO)₂]_<i>n</i> instead. The molecular structures of <b>3</b>, <b>4</b>, and <b>6</b> have been obtained by single-crystal X-ray structure determinations. The precatalytic properties of the two dicarbonyl complexes <b>3</b> and <b>4</b> toward the catalytic oxidation of cyclohexene with different oxidizing agents are discussed as well

Ruthenium Carbonyl Complexes Bearing Bis(pyrazol-1-yl)carboxylato Ligands

The syntheses of the two dicarbonyl complexes [Ru­(bdmpza)­Cl­(CO)₂] (<b>3</b>) and [Ru­(2,2-bdmpzp)­Cl­(CO)₂] (<b>4</b>), bearing a bis­(3,5-dimethylpyrazol-1-yl)­acetato (bdmpza) or a 2,2-bis­(3,5-dimethylpyrazol-1-yl)­propionato (2,2-bdmpzp) scorpionate ligand, are described. Both complexes are obtained by reacting the polymer [RuCl₂(CO)₂]_<i>n</i> with either K­[bdmpza] or K­[2,2-bdmpzp]. Reaction of the acid Hbdmpza with [Ru₃(CO)₁₂] results in the formation of two structural isomers of a hydrido complex, [Ru­(bdmpza)­H­(CO)₂] (<b>5a</b>,<b>b</b>). Under aerobic conditions conversion of [Ru­(bdmpza)­H­(CO)₂] (<b>5a</b>,<b>b</b>) to form the Ru­(I) dimer [Ru­(bdmpza)­(CO)­(μ-CO)]₂ (<b>6</b>) seems to be hindered in comparison to the case for the η⁵-C₅H₅ (Cp) analogues. Dimer <b>6</b> is obtained via a reaction of Hbdmpza with <i>catena</i>-[Ru­(OAc)­(CO)₂]_<i>n</i> instead. The molecular structures of <b>3</b>, <b>4</b>, and <b>6</b> have been obtained by single-crystal X-ray structure determinations. The precatalytic properties of the two dicarbonyl complexes <b>3</b> and <b>4</b> toward the catalytic oxidation of cyclohexene with different oxidizing agents are discussed as well

Carbon-Rich Ruthenium Allenylidene Complexes Bearing Heteroscorpionate Ligands

A series of ruthenium allenylidene complexes bearing polyaromatic substituents have been prepared starting from [Ru­(bdmpza)­Cl­(PPh₃)₂] (<b>1</b>) (bdmpza = bis­(3,5-dimethyl­pyrazol-1-yl)­acetato). Reacting <b>1</b> with 1,1-bis­(3,5-di-<i>tert</i>-butyl­phenyl)-1-methoxy-2-propyne results in the formation of two structural isomers of an allenylidene complex [Ru­(bdmpza)­Cl­(CCC­(Ph^<i>t</i>Bu₂)₂)­(PPh₃)] (<b>5A</b>/<b>5B</b>), as well as the related carbonyl complex [Ru­(bdmpza)­Cl­(CO)­(PPh₃)] (<b>4A</b>/<b>4B</b>). Conversion of 9-ethynyl-9-fluorenol leads to the corresponding allenylidene complex [Ru­(bdmpza)­Cl­(CC(FN))­(PPh₃)] (<b>7A</b>/<b>7B</b>) (FN = fluorenyl). Based on anthraquinone, a new synthetic route toward 10-ethynyl-10-hydroxy­anthracen-9-one via the trimethylsilyl-protected propargyl alcohol is described, and subsequent conversion of this compound to the allenylidene complex ([Ru­(bdmpza)­Cl­(CC(AO))­(PPh₃)] (<b>12A</b>/<b>12B</b>) (AO = anthrone) is reported. The synthetic route from 7<i>H</i>-benzo­[<i>no</i>]­tetraphen-7-one to the propargyl alcohol 7-ethynyl-7<i>H</i>-benzo­[<i>no</i>]­tetraphen-7-ol is described, which is followed by the transformation into the allenylidene complex [Ru­(bdmpza)­Cl­(CC(BT))­(PPh₃)] (<b>17A</b>/<b>17B</b>) (BT = benzotetraphene). The molecular structures of <b>4B</b>, <b>7A</b>, <b>7B</b>, <b>12A</b>, <b>12B</b>, <b>13A</b>, and <b>17A</b> have been characterized by single-crystal X-ray crystallography, and these analyses suggest that <b>17A</b> might function as a “metal-tuned organic field effect transistor”. The electrochemical properties of the allenylidene complexes have been studied via cyclic voltammetry, and time-dependent DFT calculations have been conducted to assign weak absorptions in the NIR region to forbidden MLCT transitions

Carbon-Rich Ruthenium Allenylidene Complexes Bearing Heteroscorpionate Ligands

A series of ruthenium allenylidene complexes bearing polyaromatic substituents have been prepared starting from [Ru­(bdmpza)­Cl­(PPh₃)₂] (<b>1</b>) (bdmpza = bis­(3,5-dimethyl­pyrazol-1-yl)­acetato). Reacting <b>1</b> with 1,1-bis­(3,5-di-<i>tert</i>-butyl­phenyl)-1-methoxy-2-propyne results in the formation of two structural isomers of an allenylidene complex [Ru­(bdmpza)­Cl­(CCC­(Ph^<i>t</i>Bu₂)₂)­(PPh₃)] (<b>5A</b>/<b>5B</b>), as well as the related carbonyl complex [Ru­(bdmpza)­Cl­(CO)­(PPh₃)] (<b>4A</b>/<b>4B</b>). Conversion of 9-ethynyl-9-fluorenol leads to the corresponding allenylidene complex [Ru­(bdmpza)­Cl­(CC(FN))­(PPh₃)] (<b>7A</b>/<b>7B</b>) (FN = fluorenyl). Based on anthraquinone, a new synthetic route toward 10-ethynyl-10-hydroxy­anthracen-9-one via the trimethylsilyl-protected propargyl alcohol is described, and subsequent conversion of this compound to the allenylidene complex ([Ru­(bdmpza)­Cl­(CC(AO))­(PPh₃)] (<b>12A</b>/<b>12B</b>) (AO = anthrone) is reported. The synthetic route from 7<i>H</i>-benzo­[<i>no</i>]­tetraphen-7-one to the propargyl alcohol 7-ethynyl-7<i>H</i>-benzo­[<i>no</i>]­tetraphen-7-ol is described, which is followed by the transformation into the allenylidene complex [Ru­(bdmpza)­Cl­(CC(BT))­(PPh₃)] (<b>17A</b>/<b>17B</b>) (BT = benzotetraphene). The molecular structures of <b>4B</b>, <b>7A</b>, <b>7B</b>, <b>12A</b>, <b>12B</b>, <b>13A</b>, and <b>17A</b> have been characterized by single-crystal X-ray crystallography, and these analyses suggest that <b>17A</b> might function as a “metal-tuned organic field effect transistor”. The electrochemical properties of the allenylidene complexes have been studied via cyclic voltammetry, and time-dependent DFT calculations have been conducted to assign weak absorptions in the NIR region to forbidden MLCT transitions

Carbon-Rich Ruthenium Allenylidene Complexes Bearing Heteroscorpionate Ligands

A series of ruthenium allenylidene complexes bearing polyaromatic substituents have been prepared starting from [Ru­(bdmpza)­Cl­(PPh₃)₂] (<b>1</b>) (bdmpza = bis­(3,5-dimethyl­pyrazol-1-yl)­acetato). Reacting <b>1</b> with 1,1-bis­(3,5-di-<i>tert</i>-butyl­phenyl)-1-methoxy-2-propyne results in the formation of two structural isomers of an allenylidene complex [Ru­(bdmpza)­Cl­(CCC­(Ph^<i>t</i>Bu₂)₂)­(PPh₃)] (<b>5A</b>/<b>5B</b>), as well as the related carbonyl complex [Ru­(bdmpza)­Cl­(CO)­(PPh₃)] (<b>4A</b>/<b>4B</b>). Conversion of 9-ethynyl-9-fluorenol leads to the corresponding allenylidene complex [Ru­(bdmpza)­Cl­(CC(FN))­(PPh₃)] (<b>7A</b>/<b>7B</b>) (FN = fluorenyl). Based on anthraquinone, a new synthetic route toward 10-ethynyl-10-hydroxy­anthracen-9-one via the trimethylsilyl-protected propargyl alcohol is described, and subsequent conversion of this compound to the allenylidene complex ([Ru­(bdmpza)­Cl­(CC(AO))­(PPh₃)] (<b>12A</b>/<b>12B</b>) (AO = anthrone) is reported. The synthetic route from 7<i>H</i>-benzo­[<i>no</i>]­tetraphen-7-one to the propargyl alcohol 7-ethynyl-7<i>H</i>-benzo­[<i>no</i>]­tetraphen-7-ol is described, which is followed by the transformation into the allenylidene complex [Ru­(bdmpza)­Cl­(CC(BT))­(PPh₃)] (<b>17A</b>/<b>17B</b>) (BT = benzotetraphene). The molecular structures of <b>4B</b>, <b>7A</b>, <b>7B</b>, <b>12A</b>, <b>12B</b>, <b>13A</b>, and <b>17A</b> have been characterized by single-crystal X-ray crystallography, and these analyses suggest that <b>17A</b> might function as a “metal-tuned organic field effect transistor”. The electrochemical properties of the allenylidene complexes have been studied via cyclic voltammetry, and time-dependent DFT calculations have been conducted to assign weak absorptions in the NIR region to forbidden MLCT transitions