5 research outputs found
Ruthenium Carbonyl Complexes Bearing Bis(pyrazol-1-yl)carboxylato Ligands
The syntheses of the two dicarbonyl complexes [RuÂ(bdmpza)ÂClÂ(CO)<sub>2</sub>] (<b>3</b>) and [RuÂ(2,2-bdmpzp)ÂClÂ(CO)<sub>2</sub>]
(<b>4</b>), bearing a bisÂ(3,5-dimethylpyrazol-1-yl)Âacetato (bdmpza)
or a 2,2-bisÂ(3,5-dimethylpyrazol-1-yl)Âpropionato (2,2-bdmpzp) scorpionate
ligand, are described. Both complexes are obtained by reacting the
polymer [RuCl<sub>2</sub>(CO)<sub>2</sub>]<sub><i>n</i></sub> with either KÂ[bdmpza] or KÂ[2,2-bdmpzp]. Reaction of the acid Hbdmpza
with [Ru<sub>3</sub>(CO)<sub>12</sub>] results in the formation of
two structural isomers of a hydrido complex, [RuÂ(bdmpza)ÂHÂ(CO)<sub>2</sub>] (<b>5a</b>,<b>b</b>). Under aerobic conditions
conversion of [RuÂ(bdmpza)ÂHÂ(CO)<sub>2</sub>] (<b>5a</b>,<b>b</b>) to form the RuÂ(I) dimer [RuÂ(bdmpza)Â(CO)Â(ÎŒ-CO)]<sub>2</sub> (<b>6</b>) seems to be hindered in comparison to the
case for the η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub> (Cp) analogues.
Dimer <b>6</b> is obtained via a reaction of Hbdmpza with <i>catena</i>-[RuÂ(OAc)Â(CO)<sub>2</sub>]<sub><i>n</i></sub> 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 [RuÂ(bdmpza)ÂClÂ(CO)<sub>2</sub>] (<b>3</b>) and [RuÂ(2,2-bdmpzp)ÂClÂ(CO)<sub>2</sub>]
(<b>4</b>), bearing a bisÂ(3,5-dimethylpyrazol-1-yl)Âacetato (bdmpza)
or a 2,2-bisÂ(3,5-dimethylpyrazol-1-yl)Âpropionato (2,2-bdmpzp) scorpionate
ligand, are described. Both complexes are obtained by reacting the
polymer [RuCl<sub>2</sub>(CO)<sub>2</sub>]<sub><i>n</i></sub> with either KÂ[bdmpza] or KÂ[2,2-bdmpzp]. Reaction of the acid Hbdmpza
with [Ru<sub>3</sub>(CO)<sub>12</sub>] results in the formation of
two structural isomers of a hydrido complex, [RuÂ(bdmpza)ÂHÂ(CO)<sub>2</sub>] (<b>5a</b>,<b>b</b>). Under aerobic conditions
conversion of [RuÂ(bdmpza)ÂHÂ(CO)<sub>2</sub>] (<b>5a</b>,<b>b</b>) to form the RuÂ(I) dimer [RuÂ(bdmpza)Â(CO)Â(ÎŒ-CO)]<sub>2</sub> (<b>6</b>) seems to be hindered in comparison to the
case for the η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub> (Cp) analogues.
Dimer <b>6</b> is obtained via a reaction of Hbdmpza with <i>catena</i>-[RuÂ(OAc)Â(CO)<sub>2</sub>]<sub><i>n</i></sub> 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 [RuÂ(bdmpza)ÂClÂ(PPh<sub>3</sub>)<sub>2</sub>] (<b>1</b>) (bdmpza = bisÂ(3,5-dimethylÂpyrazol-1-yl)Âacetato).
Reacting <b>1</b> with 1,1-bisÂ(3,5-di-<i>tert</i>-butylÂphenyl)-1-methoxy-2-propyne
results in the formation of two structural isomers of an allenylidene
complex [RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»CÂ(Ph<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>)Â(PPh<sub>3</sub>)] (<b>5A</b>/<b>5B</b>), as well as the related carbonyl
complex [RuÂ(bdmpza)ÂClÂ(CO)Â(PPh<sub>3</sub>)] (<b>4A</b>/<b>4B</b>). Conversion of 9-ethynyl-9-fluorenol leads to the
corresponding allenylidene complex [RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(FN))Â(PPh<sub>3</sub>)] (<b>7A</b>/<b>7B</b>) (FN = fluorenyl). Based
on anthraquinone, a new synthetic route toward 10-ethynyl-10-hydroxyÂanthracen-9-one
via the trimethylsilyl-protected propargyl alcohol is described, and
subsequent conversion of this compound to the allenylidene complex
([RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(AO))Â(PPh<sub>3</sub>)] (<b>12A</b>/<b>12B</b>) (AO = anthrone) is
reported. The synthetic route from 7<i>H</i>-benzoÂ[<i>no</i>]Âtetraphen-7-one to the propargyl alcohol 7-ethynyl-7<i>H</i>-benzoÂ[<i>no</i>]Âtetraphen-7-ol is described,
which is followed by the transformation into the allenylidene complex
[RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(BT))Â(PPh<sub>3</sub>)] (<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 âmetal-tuned organic field effect transistorâ.
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 [RuÂ(bdmpza)ÂClÂ(PPh<sub>3</sub>)<sub>2</sub>] (<b>1</b>) (bdmpza = bisÂ(3,5-dimethylÂpyrazol-1-yl)Âacetato).
Reacting <b>1</b> with 1,1-bisÂ(3,5-di-<i>tert</i>-butylÂphenyl)-1-methoxy-2-propyne
results in the formation of two structural isomers of an allenylidene
complex [RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»CÂ(Ph<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>)Â(PPh<sub>3</sub>)] (<b>5A</b>/<b>5B</b>), as well as the related carbonyl
complex [RuÂ(bdmpza)ÂClÂ(CO)Â(PPh<sub>3</sub>)] (<b>4A</b>/<b>4B</b>). Conversion of 9-ethynyl-9-fluorenol leads to the
corresponding allenylidene complex [RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(FN))Â(PPh<sub>3</sub>)] (<b>7A</b>/<b>7B</b>) (FN = fluorenyl). Based
on anthraquinone, a new synthetic route toward 10-ethynyl-10-hydroxyÂanthracen-9-one
via the trimethylsilyl-protected propargyl alcohol is described, and
subsequent conversion of this compound to the allenylidene complex
([RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(AO))Â(PPh<sub>3</sub>)] (<b>12A</b>/<b>12B</b>) (AO = anthrone) is
reported. The synthetic route from 7<i>H</i>-benzoÂ[<i>no</i>]Âtetraphen-7-one to the propargyl alcohol 7-ethynyl-7<i>H</i>-benzoÂ[<i>no</i>]Âtetraphen-7-ol is described,
which is followed by the transformation into the allenylidene complex
[RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(BT))Â(PPh<sub>3</sub>)] (<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 âmetal-tuned organic field effect transistorâ.
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 [RuÂ(bdmpza)ÂClÂ(PPh<sub>3</sub>)<sub>2</sub>] (<b>1</b>) (bdmpza = bisÂ(3,5-dimethylÂpyrazol-1-yl)Âacetato).
Reacting <b>1</b> with 1,1-bisÂ(3,5-di-<i>tert</i>-butylÂphenyl)-1-methoxy-2-propyne
results in the formation of two structural isomers of an allenylidene
complex [RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»CÂ(Ph<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>)Â(PPh<sub>3</sub>)] (<b>5A</b>/<b>5B</b>), as well as the related carbonyl
complex [RuÂ(bdmpza)ÂClÂ(CO)Â(PPh<sub>3</sub>)] (<b>4A</b>/<b>4B</b>). Conversion of 9-ethynyl-9-fluorenol leads to the
corresponding allenylidene complex [RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(FN))Â(PPh<sub>3</sub>)] (<b>7A</b>/<b>7B</b>) (FN = fluorenyl). Based
on anthraquinone, a new synthetic route toward 10-ethynyl-10-hydroxyÂanthracen-9-one
via the trimethylsilyl-protected propargyl alcohol is described, and
subsequent conversion of this compound to the allenylidene complex
([RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(AO))Â(PPh<sub>3</sub>)] (<b>12A</b>/<b>12B</b>) (AO = anthrone) is
reported. The synthetic route from 7<i>H</i>-benzoÂ[<i>no</i>]Âtetraphen-7-one to the propargyl alcohol 7-ethynyl-7<i>H</i>-benzoÂ[<i>no</i>]Âtetraphen-7-ol is described,
which is followed by the transformation into the allenylidene complex
[RuÂ(bdmpza)ÂClÂ(î»Cî»Cî»(BT))Â(PPh<sub>3</sub>)] (<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 âmetal-tuned organic field effect transistorâ.
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