10.1021/om9509397.s001
Victorio Cadierno
Victorio
Cadierno
M. Pilar Gamasa
M. Pilar
Gamasa
José Gimeno
José
Gimeno
Mercedes González-Cueva
Mercedes
González-Cueva
Elena Lastra
Elena
Lastra
Javier Borge
Javier
Borge
Santiago García-Granda
Santiago
García-Granda
Enrique Pérez-Carreño
Enrique
Pérez-Carreño
Activation of 2-Propyn-1-ol Derivatives by
Indenylruthenium(II) and -osmium(II) Complexes: X-ray
Crystal Structures of the Allenylidene Complexes
[M(CCCPh<sub>2</sub>)(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(PPh<sub>3</sub>)<sub>2</sub>][PF<sub>6</sub>]·CH<sub>2</sub>Cl<sub>2</sub> (M = Ru,
Os) and EHMO Calculations
American Chemical Society
1996
Ru
PPh 3
HC
dppm
dppe
refluxing methanol
RuCl
L 2
OH
NaPF 6
C 9 H 7
CH
potassium carbonate yields
allenylidene complexes
EHMO
2 Ph
Extended H ückel
1996-04-16 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Activation_of_2-Propyn-1-ol_Derivatives_by_Indenylruthenium_II_and_-osmium_II_Complexes_X-ray_Crystal_Structures_of_the_Allenylidene_Complexes_M_C_C_CPh_sub_2_sub_sup_5_sup_-C_sub_9_sub_H_sub_7_sub_PPh_sub_3_sub_sub_2_sub_PF_sub_6_sub_CH_sub_2_sub_Cl_sub_/3776964
The allenylidene complexes
[M(CCCR<sub>2</sub>)(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>][PF<sub>6</sub>]
(M = Ru, L = PPh<sub>3</sub>, L<sub>2</sub> =
1,2-bis(diphenylphosphino)ethane (dppe),
bis(diphenylphosphino)methane (dppm), R<sub>2</sub> =
2
Ph (<b>1a−c</b>), C<sub>12</sub>H<sub>8</sub>
(2,2‘-biphenyldiyl) (<b>2a−c</b>); M = Os, L =
PPh<sub>3</sub>, R<sub>2</sub> = 2Ph (<b>3</b>),
C<sub>12</sub>H<sub>8</sub> (<b>4</b>))
have been prepared by reaction of the complexes
[MCl(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>]
with HC⋮CC(OH)R<sub>2</sub> and
NaPF<sub>6</sub> in refluxing methanol. The crystal structures of
[M(CCCPh<sub>2</sub>)(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(PPh<sub>3</sub>)<sub>2</sub>][PF<sub>6</sub>]·CH<sub>2</sub>Cl<sub>2</sub>
(M = Ru (<b>1a</b>), Os (<b>3</b>)) were determined by X-ray
diffraction
methods. In the structures the MCCC chains are nearly
linear (M−C(1)−C(2) = 168.5(5)° (<b>1a</b>) and 169.3(4)° (<b>3</b>);
C(1)−C(2)−C(3) = 168.2(7)° (<b>1a</b>) and
168.0(5)° (<b>3</b>)) with MC(1)
distances of 1.878(5) Å (<b>1a</b>) and 1.895(4) Å
(<b>3</b>). The indenyl ligand is η<sup>5</sup>-bonded to
the metal
with the benzo ring orientated “cis” with respect to the
allenylidene group. Extended Hückel
molecular orbital calculations have been used to rationalize the
preferred “cis” orientation.
The reaction of
[RuCl(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>]
(L = PPh<sub>3</sub>, L<sub>2</sub> = dppe, dppm) with
HC⋮CCMe(OH)Ph
and NaPF<sub>6</sub> in refluxing methanol leads to the formation of
the allenylidene complexes [Ru{CCC(Me)Ph}(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>][PF<sub>6</sub>]
(<b>6a−c</b>) along with the vinylvinylidene isomers
[Ru{CC(H)C(Ph)CH<sub>2</sub>}(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>][PF<sub>6</sub>]
(L = PPh<sub>3</sub> (<b>5a</b>), L<sub>2</sub> = dppe
(<b>5b</b>), dppm (<b>5c</b>)). Only
complex <b>6a</b> could be isolated by chromatography
(SiO<sub>2</sub>) from these mixtures along with
complex <b>7a</b> obtained from the deprotonation of the
vinylvinylidene complex <b>5a</b>. The
treatment of these reaction mixtures with potassium carbonate yields
the neutral σ-enynyl
derivatives
[Ru{C⋮CC(Ph)CH<sub>2</sub>}(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>]
(<b>7a−c</b>). The monosubstituted allenylidene
complex
[Ru{CCC(H)Ph}(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(PPh<sub>3</sub>)<sub>2</sub>][PF<sub>6</sub>]
(<b>9</b>) has been prepared by the reaction
of
[RuCl(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(PPh<sub>3</sub>)<sub>2</sub>]
with HC⋮CCH(OH)Ph and NaPF<sub>6</sub> in methanol.
Under similar
reaction conditions
[RuCl(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>]
reacts with HC⋮CCH(OH)R and NaPF<sub>6</sub> to afford
the
alkenylmethoxycarbene derivatives
[Ru{C(OMe)C(H)CH(R)}(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)L<sub>2</sub>][PF<sub>6</sub>]
(L<sub>2</sub> = dppe,
R = Ph (<b>11b</b>); L<sub>2</sub> = dppm, R = Ph
(<b>11c</b>), H (<b>13</b>)).
[RuCl(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(PPh<sub>3</sub>)<sub>2</sub>]
also reacts with
HC⋮CC(OH)H<sub>2</sub> to give the hydroxyvinylidene
complex
[Ru{CCH(CH<sub>2</sub>OH)}(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(PPh<sub>3</sub>)<sub>2</sub>][PF<sub>6</sub>]
(<b>12</b>), which is stable toward the dehydration process.