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
Victorio Cadierno
M. Pilar Gamasa
José Gimeno
Mercedes González-Cueva
Elena Lastra
Javier Borge
Santiago García-Granda
Enrique Pérez-Carreño
10.1021/om9509397.s002
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_/3776961
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.
1996-04-16 00:00:00
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