5 research outputs found
Hydrolysis of Coordinated Diazoalkanes To Yield Side-On 1,2-Diazene Derivatives
No full textDiazoalkane
complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Â(N<sub>2</sub>CAr1Ar2)Â(PPh<sub>3</sub>)Â{PÂ(OR)<sub>3</sub>}]ÂBPh<sub>4</sub> [R = Me (<b>1</b>), Et (<b>2</b>); Ar1 = Ar2
= Ph (<b>a</b>); Ar1 = Ph, Ar2 = <i>p</i>-tolyl (<b>b</b>); Ar1Ar2 = C<sub>12</sub>H<sub>8</sub> (<b>c</b>)]
were prepared by allowing chloro complexes RuClÂ(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Â(PPh<sub>3</sub>)Â[PÂ(OR)<sub>3</sub>]
to react with diazoalkane Ar1Ar2CN<sub>2</sub> in ethanol. The treatment
of compounds <b>1</b> and <b>2</b> with H<sub>2</sub>O
afforded 1,2-diazene derivatives [RuÂ(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Â(η<sup>2</sup>-NHî»NH)Â(PPh<sub>3</sub>)Â{PÂ(OR)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>3</b> and <b>4</b>) and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack
by H<sub>2</sub>O on the coordinated diazoalkane is proposed. The
complexes were characterized spectroscopically (IR and NMR) and by
X-ray crystal structure determination of [RuÂ(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Â(η<sup>2</sup>-NHî»NH)Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>3</b>)
Azo Complexes of Osmium(II): Preparation and Reactivity of Organic Azide and Hydrazine Derivatives
No full textMixed-ligand
hydride complexes OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) [L = PÂ(OMe)<sub>3</sub>, PÂ(OEt)<sub>3</sub>] were prepared by allowing
OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>3</sub> (<b>1</b>) to react with
an excess of phosphite PÂ(OR)<sub>3</sub> in refluxing toluene. Dichloro
compounds OsCl<sub>2</sub>(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>3</b>,<b> 4</b>) were also prepared by reacting <b>1</b>, <b>2</b> with HCl. Treatment of hydrides OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>), first with triflic acid and
then with an excess of RN<sub>3</sub> afforded organic azide complexes
[OsClÂ(η<sup>1</sup>-N<sub>3</sub>R)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>5</b>â<b>7</b>) [R
= 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>, C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>, C<sub>6</sub>H<sub>5</sub>; L
= PÂ(OEt)<sub>3</sub>]. Benzylazide complexes react in CH<sub>2</sub>Cl<sub>2</sub>/ethanol solution, leading to the imine derivative
[OsClÂ(CO)Â{η<sup>1</sup>-NHî»CÂ(H)ÂC<sub>6</sub>H<sub>4</sub>-4-CH<sub>3</sub>}Â(PPh<sub>3</sub>)<sub>2</sub>{PÂ(OEt)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>8b</b>). Hydrazine complexes [OsClÂ(CO)Â(RNHNH<sub>2</sub>)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>9</b>â<b>11</b>) [R = H, CH<sub>3</sub>, C<sub>6</sub>H<sub>5</sub>; L = PÂ(OMe)<sub>3</sub>, PÂ(OEt)<sub>3</sub>] were prepared
by allowing hydride species OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) to react first with triflic acid and then with
an excess of hydrazine. Aryldiazene derivatives [OsClÂ(CO)Â(ArNî»NH)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>12</b>,<b> 13</b>) were also prepared following two different methods: (i) by oxidizing
arylhydrazine [OsClÂ(C<sub>6</sub>H<sub>5</sub>NHNH<sub>2</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>11</b>) with PbÂ(OAc)<sub>4</sub> in CH<sub>2</sub>Cl<sub>2</sub> at â30 °C; (ii)
by allowing hydride species OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) to react with aryldiazonium cations ArN<sub>2</sub><sup>+</sup> (Ar = C<sub>6</sub>H<sub>5</sub>, 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) in CH<sub>2</sub>Cl<sub>2</sub>. The complexes
were characterized spectroscopically and by X-ray crystal structure
determination of OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>[PÂ(OEt)<sub>3</sub>] (<b>2b</b>) and [OsClÂ{η<sup>1</sup>-NHî»CÂ(H)ÂC<sub>6</sub>H<sub>4</sub>-4-CH<sub>3</sub>}Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>{PÂ(OEt)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>8b</b>)
Preparation of Diazoalkane Complexes of Ruthenium and Their Cyclization Reactions with Alkenes and Alkynes
No full textThe
diazoalkane complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(N<sub>2</sub>CAr1Ar2)Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>1</b>â<b>5</b>: Ar1 = Ar2 = Ph (<b>a</b>),
Ar1 = Ph and Ar2 = <i>p-</i>tolyl (<b>b</b>), Ar1Ar2
= C<sub>12</sub>H<sub>8</sub> (<b>c</b>), Ar1 = Ph and Ar2 =
PhCO (<b>d</b>); L = PPh<sub>3</sub> (<b>1</b>), PÂ(OMe)<sub>3</sub> (<b>2</b>), PÂ(OEt)<sub>3</sub> (<b>3</b>), PPhÂ(OEt)<sub>2</sub> (<b>4</b>), Bu<sup><i>t</i></sup>NC (<b>5</b>)) were prepared by allowing the chloro compounds RuClÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(PPh<sub>3</sub>)Â(L) to react
with the diazoalkanes Ar1Ar2CN<sub>2</sub> in ethanol. Treatment of
complexes <b>1</b>â<b>5</b> with ethylene (CH<sub>2</sub>î»CH<sub>2</sub>) under mild conditions (1 atm, room
temperature) led not only to the η<sup>2</sup>-ethylene complexes
[RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(η<sup>2</sup>-CH<sub>2</sub>î»CH<sub>2</sub>)Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>10</b>â<b>14</b>) but also to dipolar
(3 + 2) cycloaddition, affording the 4,5-dihydro-3<i>H</i>-pyrazole derivatives [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(Ar1Ar2)ÂCH<sub>2</sub>CH<sub>2</sub>}Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>6</b>â<b>9</b>). Acrylonitrile (CH<sub>2</sub>î»CÂ(H)ÂCN) reacted with diazoalkane
complexes <b>2</b> and <b>3</b> to give the 1<i>H</i>-pyrazoline derivatives [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»CÂ(CN)ÂCH<sub>2</sub>CÂ(Ar1Ar2)NH}Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>19</b>, <b>20</b>). However,
reactions with propylene (CH<sub>2</sub>î»CÂ(H)ÂCH<sub>3</sub>), maleic anhydride (ma, CHî»CHCOÂ(O)CO) and dimethyl maleate
(dmm, CH<sub>3</sub>OCOCHî»CHOCOCH<sub>3</sub>) led to the η<sup>2</sup>-alkene complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(η<sup>2</sup>-R1CHî»CHR2)Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>17</b>â<b>22</b>). Treatment of the
diazoalkane complexes <b>1</b> and <b>2</b> with acetylene
CHîŒCH under mild conditions (1 atm, room temperature) led to
dipolar cycloaddition, affording the 3<i>H</i>-pyrazole
complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(Ar1Ar2)ÂCHî»CH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>24</b>), whereas reactions with the terminal alkynes PhCîŒCH and
Bu<sup><i>t</i></sup>CîŒCH gave the vinylidene derivatives
[RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{î»Cî»CÂ(H)ÂR}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>25</b>,<b> 26</b>). The alkyl propiolates HCîŒCCOOR1 (R1 = Me, Et)
also reacted with complexes <b>2</b> to give the 3<i>H</i>-pyrazole complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(Ar1Ar2)ÂCÂ(COOR1)î»CH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>27</b>,<b> 28</b>). The complexes were characterized by spectroscopy
and by X-ray crystal structure determinations of [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»CÂ(CN)ÂCH<sub>2</sub>CÂ(Ph)Â(<i>p</i>-tolyl)NH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>19b</b>), [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>2</sup>-CHî»CHCOÂ(O)CO}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>21</b>), and [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(C<sub>12</sub>H<sub>8</sub>)ÂCHî»CH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>24c</b>)
Preparation of Diazoalkane Complexes of Ruthenium and Their Cyclization Reactions with Alkenes and Alkynes
No full textThe
diazoalkane complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(N<sub>2</sub>CAr1Ar2)Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>1</b>â<b>5</b>: Ar1 = Ar2 = Ph (<b>a</b>),
Ar1 = Ph and Ar2 = <i>p-</i>tolyl (<b>b</b>), Ar1Ar2
= C<sub>12</sub>H<sub>8</sub> (<b>c</b>), Ar1 = Ph and Ar2 =
PhCO (<b>d</b>); L = PPh<sub>3</sub> (<b>1</b>), PÂ(OMe)<sub>3</sub> (<b>2</b>), PÂ(OEt)<sub>3</sub> (<b>3</b>), PPhÂ(OEt)<sub>2</sub> (<b>4</b>), Bu<sup><i>t</i></sup>NC (<b>5</b>)) were prepared by allowing the chloro compounds RuClÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(PPh<sub>3</sub>)Â(L) to react
with the diazoalkanes Ar1Ar2CN<sub>2</sub> in ethanol. Treatment of
complexes <b>1</b>â<b>5</b> with ethylene (CH<sub>2</sub>î»CH<sub>2</sub>) under mild conditions (1 atm, room
temperature) led not only to the η<sup>2</sup>-ethylene complexes
[RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(η<sup>2</sup>-CH<sub>2</sub>î»CH<sub>2</sub>)Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>10</b>â<b>14</b>) but also to dipolar
(3 + 2) cycloaddition, affording the 4,5-dihydro-3<i>H</i>-pyrazole derivatives [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(Ar1Ar2)ÂCH<sub>2</sub>CH<sub>2</sub>}Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>6</b>â<b>9</b>). Acrylonitrile (CH<sub>2</sub>î»CÂ(H)ÂCN) reacted with diazoalkane
complexes <b>2</b> and <b>3</b> to give the 1<i>H</i>-pyrazoline derivatives [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»CÂ(CN)ÂCH<sub>2</sub>CÂ(Ar1Ar2)NH}Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>19</b>, <b>20</b>). However,
reactions with propylene (CH<sub>2</sub>î»CÂ(H)ÂCH<sub>3</sub>), maleic anhydride (ma, CHî»CHCOÂ(O)CO) and dimethyl maleate
(dmm, CH<sub>3</sub>OCOCHî»CHOCOCH<sub>3</sub>) led to the η<sup>2</sup>-alkene complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â(η<sup>2</sup>-R1CHî»CHR2)Â(PPh<sub>3</sub>)Â(L)]ÂBPh<sub>4</sub> (<b>17</b>â<b>22</b>). Treatment of the
diazoalkane complexes <b>1</b> and <b>2</b> with acetylene
CHîŒCH under mild conditions (1 atm, room temperature) led to
dipolar cycloaddition, affording the 3<i>H</i>-pyrazole
complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(Ar1Ar2)ÂCHî»CH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>24</b>), whereas reactions with the terminal alkynes PhCîŒCH and
Bu<sup><i>t</i></sup>CîŒCH gave the vinylidene derivatives
[RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{î»Cî»CÂ(H)ÂR}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>25</b>,<b> 26</b>). The alkyl propiolates HCîŒCCOOR1 (R1 = Me, Et)
also reacted with complexes <b>2</b> to give the 3<i>H</i>-pyrazole complexes [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(Ar1Ar2)ÂCÂ(COOR1)î»CH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>27</b>,<b> 28</b>). The complexes were characterized by spectroscopy
and by X-ray crystal structure determinations of [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»CÂ(CN)ÂCH<sub>2</sub>CÂ(Ph)Â(<i>p</i>-tolyl)NH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>19b</b>), [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>2</sup>-CHî»CHCOÂ(O)CO}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>21</b>), and [RuÂ(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Â{η<sup>1</sup>-Nî»NCÂ(C<sub>12</sub>H<sub>8</sub>)ÂCHî»CH}Â(PPh<sub>3</sub>)Â{PÂ(OMe)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>24c</b>)
Azo Complexes of Osmium(II): Preparation and Reactivity of Organic Azide and Hydrazine Derivatives
No full textMixed-ligand
hydride complexes OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) [L = PÂ(OMe)<sub>3</sub>, PÂ(OEt)<sub>3</sub>] were prepared by allowing
OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>3</sub> (<b>1</b>) to react with
an excess of phosphite PÂ(OR)<sub>3</sub> in refluxing toluene. Dichloro
compounds OsCl<sub>2</sub>(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>3</b>,<b> 4</b>) were also prepared by reacting <b>1</b>, <b>2</b> with HCl. Treatment of hydrides OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>), first with triflic acid and
then with an excess of RN<sub>3</sub> afforded organic azide complexes
[OsClÂ(η<sup>1</sup>-N<sub>3</sub>R)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>5</b>â<b>7</b>) [R
= 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>, C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>, C<sub>6</sub>H<sub>5</sub>; L
= PÂ(OEt)<sub>3</sub>]. Benzylazide complexes react in CH<sub>2</sub>Cl<sub>2</sub>/ethanol solution, leading to the imine derivative
[OsClÂ(CO)Â{η<sup>1</sup>-NHî»CÂ(H)ÂC<sub>6</sub>H<sub>4</sub>-4-CH<sub>3</sub>}Â(PPh<sub>3</sub>)<sub>2</sub>{PÂ(OEt)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>8b</b>). Hydrazine complexes [OsClÂ(CO)Â(RNHNH<sub>2</sub>)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>9</b>â<b>11</b>) [R = H, CH<sub>3</sub>, C<sub>6</sub>H<sub>5</sub>; L = PÂ(OMe)<sub>3</sub>, PÂ(OEt)<sub>3</sub>] were prepared
by allowing hydride species OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) to react first with triflic acid and then with
an excess of hydrazine. Aryldiazene derivatives [OsClÂ(CO)Â(ArNî»NH)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>12</b>,<b> 13</b>) were also prepared following two different methods: (i) by oxidizing
arylhydrazine [OsClÂ(C<sub>6</sub>H<sub>5</sub>NHNH<sub>2</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L]ÂBPh<sub>4</sub> (<b>11</b>) with PbÂ(OAc)<sub>4</sub> in CH<sub>2</sub>Cl<sub>2</sub> at â30 °C; (ii)
by allowing hydride species OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>L (<b>2</b>) to react with aryldiazonium cations ArN<sub>2</sub><sup>+</sup> (Ar = C<sub>6</sub>H<sub>5</sub>, 4-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) in CH<sub>2</sub>Cl<sub>2</sub>. The complexes
were characterized spectroscopically and by X-ray crystal structure
determination of OsHClÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>[PÂ(OEt)<sub>3</sub>] (<b>2b</b>) and [OsClÂ{η<sup>1</sup>-NHî»CÂ(H)ÂC<sub>6</sub>H<sub>4</sub>-4-CH<sub>3</sub>}Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>{PÂ(OEt)<sub>3</sub>}]ÂBPh<sub>4</sub> (<b>8b</b>)
