4 research outputs found
Multimetallic Alkenyl Complexes Bearing Macrocyclic Dithiocarbamate Ligands
No full textThe aza-crown ether compounds 1-aza-15-crown-5
and 1,10-diaza-18-crown-6
react with sodium hydroxide and carbon disulfide to provide the dithiocarbamates
[15]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na and NaS<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na in good yield. The complexes [MRClÂ(CO)Â(L)Â(PPh<sub>3</sub>)<sub>2</sub>] (M = Ru, R = H, CHî—»CHC<sub>6</sub>H<sub>4</sub>Me-4, CHî—»CHBu<sup>t</sup>, CHî—»CH-pyrenyl-1,
CÂ(Cî—¼CPh)î—»CHPh; M = Os, R = H, CHî—»CH-pyrenyl-1;
L = 2,1,3-benzothiadiazole or no ligand) undergo reaction with [15]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na and NaS<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na to yield [MRÂ(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] and [{MRÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>)], respectively. In a similar manner, <i>cis</i>-[RuCl<sub>2</sub>(dppm)<sub>2</sub>] provides [RuÂ(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(dppm)<sub>2</sub>]<sup>+</sup> and [{RuÂ(dppm)<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>)]<sup>2+</sup>, respectively. Reaction of [RuÂ(CHî—»CHC<sub>6</sub>H<sub>4</sub>Me-4)Â(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] with excess HCî—¼CBu<sup>t</sup> leads to the formation of the alkynyl complex [RuÂ(Cî—¼CBu<sup>t</sup>)Â(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>]. Treatment of [OsHClÂ(CO)Â(BTD)Â(PPh<sub>3</sub>)<sub>2</sub>] with [HCî—¼C-bpyReClÂ(CO)<sub>3</sub>] results
in the bimetallic compound [OsÂ{CHî—»CH-bpyReClÂ(CO)<sub>3</sub>}ÂClÂ(CO)Â(BTD)Â(PPh<sub>3</sub>)<sub>2</sub>]. This reacts
with [15]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na and NaS<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na to yield [OsÂ{CHî—»CH-bpyReClÂ(CO)<sub>3</sub>}Â(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] and [{OsÂ{CHî—»CH-bpyReClÂ(CO)<sub>3</sub>}Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>)], respectively. NMR studies
provide information on the selectivity of binding of Li and Na ions.
The structures of [RuRÂ(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] (R = H, CHî—»CHC<sub>6</sub>H<sub>4</sub>Me-4, CHî—»CH-pyrenyl-1) are also reported
Multimetallic Alkenyl Complexes Bearing Macrocyclic Dithiocarbamate Ligands
No full textThe aza-crown ether compounds 1-aza-15-crown-5
and 1,10-diaza-18-crown-6
react with sodium hydroxide and carbon disulfide to provide the dithiocarbamates
[15]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na and NaS<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na in good yield. The complexes [MRClÂ(CO)Â(L)Â(PPh<sub>3</sub>)<sub>2</sub>] (M = Ru, R = H, CHî—»CHC<sub>6</sub>H<sub>4</sub>Me-4, CHî—»CHBu<sup>t</sup>, CHî—»CH-pyrenyl-1,
CÂ(Cî—¼CPh)î—»CHPh; M = Os, R = H, CHî—»CH-pyrenyl-1;
L = 2,1,3-benzothiadiazole or no ligand) undergo reaction with [15]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na and NaS<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na to yield [MRÂ(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] and [{MRÂ(CO)Â(PPh<sub>3</sub>)<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>)], respectively. In a similar manner, <i>cis</i>-[RuCl<sub>2</sub>(dppm)<sub>2</sub>] provides [RuÂ(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(dppm)<sub>2</sub>]<sup>+</sup> and [{RuÂ(dppm)<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>)]<sup>2+</sup>, respectively. Reaction of [RuÂ(CHî—»CHC<sub>6</sub>H<sub>4</sub>Me-4)Â(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] with excess HCî—¼CBu<sup>t</sup> leads to the formation of the alkynyl complex [RuÂ(Cî—¼CBu<sup>t</sup>)Â(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>]. Treatment of [OsHClÂ(CO)Â(BTD)Â(PPh<sub>3</sub>)<sub>2</sub>] with [HCî—¼C-bpyReClÂ(CO)<sub>3</sub>] results
in the bimetallic compound [OsÂ{CHî—»CH-bpyReClÂ(CO)<sub>3</sub>}ÂClÂ(CO)Â(BTD)Â(PPh<sub>3</sub>)<sub>2</sub>]. This reacts
with [15]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na and NaS<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>Na to yield [OsÂ{CHî—»CH-bpyReClÂ(CO)<sub>3</sub>}Â(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] and [{OsÂ{CHî—»CH-bpyReClÂ(CO)<sub>3</sub>}Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>}<sub>2</sub>(S<sub>2</sub>CN-[18]ÂaneO<sub>4</sub>-NCS<sub>2</sub>)], respectively. NMR studies
provide information on the selectivity of binding of Li and Na ions.
The structures of [RuRÂ(S<sub>2</sub>CN-[15]ÂaneO<sub>4</sub>)Â(CO)Â(PPh<sub>3</sub>)<sub>2</sub>] (R = H, CHî—»CHC<sub>6</sub>H<sub>4</sub>Me-4, CHî—»CH-pyrenyl-1) are also reported
The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties
No full textThe versatile rhenium complex [ReCl(CO)3(bpyCuCH)] (HCuCbpy = 5-ethynyl-2,2’-bipyridine) is used to
generate a series of bimetallic complexes through the hydrometallation of [MHCl(CO)(BTD)(PPh3)2] (M =
Ru, Os; BTD = 2,1,3-benzothiadiazole). The ruthenium complex [Ru{CHvCH-bpyReCl(CO)3}Cl(BTD)(CO)
(PPh3)2] was characterised structurally. Ligand exchange reactions with bifunctional linkers bearing
oxygen and sulfur donors provide access to tetra- and pentametallic complexes such as [{M{CHvCHbpyReCl(
CO)3}(CO)(PPh3)2}2(S2CNC4H8NCS2)] and Fe[C5H4CO2M{CHvCH-bpyReCl(CO)3}(CO)(PPh3)2]2.
The effect of the group 8 metal on the photophysical properties of the rhenium centre was investigated
using the complexes [Ru{CHvCH-bpyReCl(CO)3}Cl(BTD)(CO)(PPh3)2] and [M{CHvCH-bpyReCl(CO)3}
{S2P(OEt)2}(CO)(PPh3)2] (M = Ru, Os). This revealed the quenching of the rhenium-based emission in
favour of weak radiative processes based on the Ru and Os centres. The potential for exploiting this effect
is illustrated by the reaction of [Ru{CHvCH-bpyReCl(CO)3}Cl(CO)(BTD)(PPh3)2] with carbon monoxide,
which results in a 5-fold fluorescence enhancement in the dicarbonyl product, [Ru{CHvCH-bpyReCl
(CO)3}Cl(CO)2(PPh3)2], as the quenching effect is disrupted
