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Iridium complexes featuring a tridentate SiPSi ligand: from dimeric to monomeric 14, 16 or 18-electron species
Ist Teil von
Dalton transactions : an international journal of inorganic chemistry, 2019-09, Vol.48 (37), p.141-1418
Ort / Verlag
England: Royal Society of Chemistry
Erscheinungsjahr
2019
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
In the solid state, the dinuclear iridium complex [μ-Cl-Ir(SiMe
2
CH
2
-
o
-C
6
H
4
)
2
PPh]
2
,
1
, is shown by X-ray diffraction to bear dibenzylsilylphosphine ligands in SiPSi tridentate coordination modes as well as chloride bridges. In C
6
D
6
solution,
1
dissociates into the 14-electron species [IrCl(SiMe
2
CH
2
-
o
-C
6
H
4
)
2
PPh] prone to coordinate one or two L-type ligands such as PR
3
(R = Cy, Ph, OEt), CO and CH
3
CN giving rise to the corresponding mononuclear 16- or 18-electron complexes [IrCl(SiMe
2
CH
2
-
o
-C
6
H
4
)
2
PPh(L)
x
] (
x
= 1, 2) as evidenced by X-ray and NMR studies. The dinuclear structure is retained upon reaction with Et
3
SiH which results in the formation of [μ-Cl,μ-H-Ir
2
{(SiMe
2
CH
2
-
o
-C
6
H
4
)
2
PPh}
2
] with a bridging hydride. On the basis of NMR studies, the reaction of the triphenylphosphine complex [IrCl(SiMe
2
CH
2
-
o
-C
6
H
4
)
2
PPh(PPh
3
)] with LiBHEt
3
leads to the hydride complex [IrH(SiMe
2
CH
2
-
o
-C
6
H
4
)(η
2
-H-SiMe
2
CH-
o
-C
6
H
4
)PPh(PPh
3
)] in which one SiPSi ligand has been transformed and is now bonded to iridium in a tetradentate mode
via
P, Si, an agostic Si-H bond, and C of a methine as a result of the activation of one methylene group.
Dimer [Ir{P(
o
-C
6
H
4
CH
2
SiMe
2
)
2
Ph}(μ-Cl)]
2
featuring tricoordinate phosphinodisilyl ligands dissociates in solution to the reactive 14 electron monomer [Ir(SiPSi)Cl].