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Reactivity of the phosphinito bridged Pt(i) complex [(PHCy2)Pt(μ-PCy2){κ2P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) towards Au(i) and Ag(i) electrophilesDedicated to Emeritus Professor Juan Forniés on the occasion of his 65th birthday.Electronic supplementary information (ESI) available: 31P{1H} NMR spectrum of 4, 7, [9]X (X = OTf, ClO4, BF4, Cl), [10]OTf; 31P NMR spectrum of 4, 31P{1H} NOESY-EXSY of [10]OTf, 195Pt{1H} NMR spectrum of 4, [6]OTf, 7, [9]OTf; HRMS data of 4, [6]+, [7 + H]+, [8 + H]+, 9+, 9-Cl
The reactivity of the phosphinito bridged Pt( i ) complex [(PHCy 2 )Pt 1 (μ-PCy 2 ){κ 2 P , O -μ-P(O)Cy 2 }Pt 2 (PHCy 2 )]( Pt-Pt ) ( 1 ) towards Au( i ) and Ag( i ) electrophiles was explored. Treatment of 1 with AuCl yielded the dichloro Pt( ii ) complex [(Cl)(PHCy 2 )Pt(μ-PCy 2 ){κ 2 P , O -μ-P(O...
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| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
| Online Access: | Get full text |
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| Summary: | The reactivity of the phosphinito bridged Pt(
i
) complex [(PHCy
2
)Pt
1
(μ-PCy
2
){κ
2
P
,
O
-μ-P(O)Cy
2
}Pt
2
(PHCy
2
)](
Pt-Pt
) (
1
) towards Au(
i
) and Ag(
i
) electrophiles was explored. Treatment of
1
with AuCl yielded the dichloro Pt(
ii
) complex [(Cl)(PHCy
2
)Pt(μ-PCy
2
){κ
2
P
,
O
-μ-P(O)Cy
2
}Pt(Cl)(PHCy
2
)] (
4
), while [Au(PPh
3
)Cl] in thf (or toluene) caused ligand exchange resulting in the formation of [(PPh
3
)Pt(μ-PCy
2
){κ
2
P
,
O
-μ-P(O)Cy
2
}Pt(PHCy
2
)](
Pt-Pt
) (
7
) and [(PPh
3
)Pt(μ-PCy
2
){κ
2
P
,
O
-μ-P(O)Cy
2
}Pt(PPh
3
)](
Pt-Pt
) (
8
). With [Au(PPh
3
)OTf] (independently from the solvent) or with [Au(PPh
3
)Cl] (only in dichloromethane), reaction with
1
gave [(PHCy
2
)Pt
1
(μ-PCy
2
){κ
2
P
,
O
-μ-P(O)Cy
2
}Pt
2
{μ-Au(PPh
3
)}(PHCy
2
)]X(
Pt-Pt
) ([
6
]X, X = OTf, Cl) clusters in which the [Au(PPh
3
)] moiety bridges the μP-Pt
2
bond. The [Ag(PPh
3
)]
+
electrophile attacks complex
1
selectively at the Pt
2
-μP bond to afford, at low T, the cationic cluster [(PHCy
2
)Pt
1
(μ-PCy
2
){κ
2
P
,
O
-μ-P(O)Cy
2
}Pt
2
{μ-Ag(PPh
3
)}(PHCy
2
)]
+
(
Pt-Pt
) (
10
+
) in which the [Ag(PPh
3
)]
+
moiety bridges the μP-Pt
2
bond. Clusters analogous to
10
+
, but without PPh
3
bonded to Ag, are obtained from reactions of
1
with AgOTf, AgBF
4
, AgClO
4
and AgCl.
The Pt(
i
) complex depicted in the figure reacts with M(PPh
3
)
n
X electrophiles (M = Ag, Au;
n
= 1, 0; X = Cl, OTf, BF
4
, ClO
4
) to give various types of MPt
2
clusters. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c2dt32393a |