Synthesis of Silver(I) and Gold(I) Complexes Containing
Enantiopure Pybox Ligands. First Assays on the Silver(I)-Catalyzed
Asymmetric Addition of Alkynes to Imines
Gustavo
M. Borrajo-Calleja
Eire de Julián
Esther Bayón
Josefina Díez
Elena Lastra
Isabel Merino
M. Pilar Gamasa
10.1021/acs.inorgchem.6b01323.s001
https://acs.figshare.com/articles/dataset/Synthesis_of_Silver_I_and_Gold_I_Complexes_Containing_Enantiopure_Pybox_Ligands_First_Assays_on_the_Silver_I_-Catalyzed_Asymmetric_Addition_of_Alkynes_to_Imines/3546060
Dinuclear complexes
[Ag<sub>2</sub>(CF<sub>3</sub>SO<sub>3</sub>){(<i>S</i>,<i>S</i>)-<sup><i>i</i></sup>Pr-pybox}<sub>2</sub>][CF<sub>3</sub>SO<sub>3</sub>] (<b>1</b>), [Ag<sub>2</sub>(R-pybox)<sub>2</sub>][X]<sub>2</sub> [R-pybox = 2,6-bis[4-(<i>S</i>)-isopropyloxazolin-2-yl]pyridine
(<i>S</i>,<i>S</i>)-<sup><i>i</i></sup>Pr-pybox and X = PF<sub>6</sub> (<b>2</b>) and BF<sub>4</sub> (<b>3</b>); R-pybox = 2,6-bis[(3a<i>S</i>,8a<i>R</i>)-8,8a-dihydro-3a<i>H</i>-indeno[1,2-<i>d</i>]oxazol-2-yl]pyridine (3a<i>S</i>,3a′<i>S</i>,8a<i>R</i>,8a′<i>R</i>)-indane-pybox
and X = CF<sub>3</sub>SO<sub>3</sub> (<b>4</b>)], [Ag<sub>2</sub>{(<i>S</i>,<i>S</i>)-<sup><i>i</i></sup>Pr-pybox}{(3a<i>S</i>,3a′<i>S</i>,8a<i>R</i>,8a′<i>R</i>)-indane-pybox}][CF<sub>3</sub>SO<sub>3</sub>]<sub>2</sub> (<b>5</b>), and [Ag<sub>2</sub>(R-pybox)<sub>3</sub>][X]<sub>2</sub> [R-pybox = (3a<i>S</i>,3a′<i>S</i>,8a<i>R</i>,8a′<i>R</i>)-indane-pybox and X = CF<sub>3</sub>SO<sub>3</sub> (<b>10</b>), SF<sub>6</sub> (<b>11</b>), and PF<sub>6</sub> (<b>12</b>)] as well as mononuclear complexes [Ag(R-pybox)<sub>2</sub>][X] [R-pybox = (<i>S</i>,<i>S</i>)-<sup><i>i</i></sup>Pr-pybox and X = SbF<sub>6</sub> (<b>6</b>),
PF<sub>6</sub> (<b>7</b>), and BF<sub>4</sub> (<b>8</b>); R-pybox = (3a<i>S</i>,3a′<i>S</i>,8a<i>R</i>,8a′<i>R</i>)-indane-pybox) and X = BF<sub>4</sub> (<b>9</b>)] have been prepared by the reaction of the
corresponding silver salts and pybox ligands using the appropriate
molar ratio conditions. The first gold(I)/pybox complex [Au<sub>6</sub>Cl<sub>4</sub>{(<i>S</i>,<i>S</i>)-<sup><i>i</i></sup>Pr-pybox}<sub>4</sub>][AuCl<sub>2</sub>]<sub>2</sub> (<b>13</b>) has been synthesized by the reaction of [AuCl{S(CH<sub>3</sub>)<sub>2</sub>}] and (<i>S</i>,<i>S</i>)-<sup><i>i</i></sup>Pr-pybox (1:1 molar ratio) in acetonitrile.
The structures of the dinuclear (<b>1</b>, <b>4</b>, <b>5</b>, <b>10</b>, and <b>11</b>) and mononuclear (<b>6</b> and <b>9</b>) silver complexes and the hexanuclear
gold complex <b>13</b> have been determined by single-crystal
X-ray diffraction analysis. These studies have been complemented with
a solution-state study by NMR spectroscopy, which included structure
elucidation, variable-temperature measurements, and diffusion studies
using diffusion-ordered spectroscopy (DOSY; for complexes <b>1</b>, <b>4</b>, <b>10</b>, and <b>12</b>). Complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>10</b> have
been assayed as catalysts in the asymmetric addition of phenylacetylene
to <i>N</i>-benzylideneaniline.
2016-08-08 13:48:38
BF 4
Ag 2
Imines Dinuclear complexes
Pr-pybox
PF 6
SF
DOSY
R-pybox
indane-pybox
CF 3
molar ratio conditions
single-crystal X-ray diffraction analysis
NMR