1,1-Ethylenedithiolato Complexes of Palladium(II) and Platinum(II) with
Isocyanide and Carbene Ligands
José Vicente
María Teresa Chicote
Sonia Huertas
Peter G. Jones
10.1021/ic0343758.s002
https://acs.figshare.com/articles/dataset/1_1-Ethylenedithiolato_Complexes_of_Palladium_II_and_Platinum_II_with_Isocyanide_and_Carbene_Ligands/3612507
The reactions of [Tl<sub>2</sub>{S<sub>2</sub>CC{C(O)Me}<sub>2</sub>}]<i><sub>n</sub></i> with [MCl<sub>2</sub>(NCPh)<sub>2</sub>] and CNR (1:1:2) give complexes [M{η<sup>2</sup>-S<sub>2</sub>CC{C(O)Me}<sub>2</sub>}(CNR)<sub>2</sub>] [R = <sup>t</sup>Bu, M = Pd (<b>1a</b>), Pt (<b>1b</b>); R = C<sub>6</sub>H<sub>3</sub>Me<sub>2</sub>-2,6 (Xy), M = Pd (<b>2a</b>), Pt (<b>2b</b>)]. Compound
<b>1b</b> reacts with AgClO<sub>4</sub> (1:1) to give [{Pt(CN<sup>t</sup>Bu)<sub>2</sub>}<sub>2</sub>Ag<sub>2</sub>{μ<sup>2</sup>,η<sup>2</sup>-(<i>S</i>,<i>S</i>‘)-{S<sub>2</sub>CC{C(O)Me}<sub>2</sub>}<sub>2</sub>}](ClO<sub>4</sub>)<sub>2</sub> (<b>3</b>). The reactions
of <b>1</b> or <b>2</b> with diethylamine give mixed isocyanide carbene complexes [M{η<sup>2</sup>-S<sub>2</sub>CC{C(O)Me}<sub>2</sub>}(CNR){C(NEt<sub>2</sub>)(NHR)}] [R = <sup>t</sup>Bu, M = Pd (<b>4a</b>), Pt (<b>4b</b>); R = Xy, M = Pd (<b>5a</b>), Pt (<b>5b</b>)] regardless of the molar ratio
of the reagents. The same complexes react with an excess of ammonia to give [M{η<sup>2</sup>-(<i>S</i>,<i>S</i>‘)-S<sub>2</sub>CC{C(O)Me}<sub>2</sub>}(CN<sup>t</sup>Bu){C(NH<sub>2</sub>)(NH<sup>t</sup>Bu)}] [M = Pd (<b>6a</b>), Pt (<b>6b</b>)] or [M{η<sup>2</sup>-(<i>S</i>,<i>S</i>‘)-S<sub>2</sub>CC{C(O)Me}<sub>2</sub>}{C(NH<sub>2</sub>)(NHXy)}<sub>2</sub>] [M = Pd
(<b>7a</b>), Pt (<b>7b</b>)] probably depending on steric factors. The crystal structures of <b>2b</b>, <b>4a</b>, and <b>4b </b>have been determined.
Compounds <b>4a</b> and <b>4b</b> are isostructural. They all display distorted square planar metal environments and chelating
planar <i>E,Z</i>-2,2-diacetyl-1,1-ethylenedithiolato ligands that coordinate through the sulfur atoms.
2003-06-11 00:00:00
C 6 H 3
NHR
t Bu
4 b
Pt
Pd
NH
CN
CNR
isocyanide carbene complexes