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