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Heavy metalla vinyl-cations show metal-Lewis acid cooperativity in reaction with small molecules (NH, NH, HO, H)
Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe 3 ) 3 ] [E = Ge ( 1 ), Sn ( 2 )] and [Ar*E(Cl)IrH(PMe 3 ) 3 ] gives the salts [TbbEIrH(PMe 3 ) 3 ][BAr F 4 ] [E = Ge ( 3 ), Sn ( 4 )] and [Ar*EIrH(PMe 3 ) 3 ][BAr F 4 ] [E = Ge ( 3′ ), E = Sn ( 4′ )] (Tbb = 2,6-[CH(SiMe 3 ) 2 ] 2 -4-( t...
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| Published in: | Chemical science (Cambridge) 2023-01, Vol.14 (3), p.514-524 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
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| Summary: | Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe
3
)
3
] [E = Ge (
1
), Sn (
2
)] and [Ar*E(Cl)IrH(PMe
3
)
3
] gives the salts [TbbEIrH(PMe
3
)
3
][BAr
F
4
] [E = Ge (
3
), Sn (
4
)] and [Ar*EIrH(PMe
3
)
3
][BAr
F
4
] [E = Ge (
3′
), E = Sn (
4′
)] (Tbb = 2,6-[CH(SiMe
3
)
2
]
2
-4-(
t
-Bu)C
6
H
2
, Ar* = 2,6-Trip
2
C
6
H
3
, Trip = 2,4,6-triisopropylphenyl). Bonding analysis suggests their most suitable description as metalla-tetrela vinyl cations with an Ir&z.dbd;E double bond and a near linear coordination at the Ge/Sn atoms. Cationic complexes
3
and
4
oxidatively add NH
3
, N
2
H
4
, H
2
O, HCl, and H
2
selectively to give: [TbbGe(NH
2
)IrH
2
(PMe
3
)
3
][BAr
F
4
] (
5
), [TbbE(NHNH
2
)IrH
2
(PMe
3
)
3
][BAr
F
4
] [E = Ge (
7
), Sn (
8
)], [TbbE(OH)IrH
2
(PMe
3
)
3
][BAr
F
4
] [E = Ge (
9
), Sn (
10
)], [TbbE(Cl)IrH
2
(PMe
3
)
3
][BAr
F
4
] [E = Ge (
11a
), Sn (
12a
)], [TbbGe(H)IrH
2
(PMe
3
)
3
][BAr
F
4
] (
13
), [TbbSn(μ-H
3
)Ir(PMe
3
)
3
][BAr
F
4
] (
14
), and [TbbSn(H)IrH
2
(PMe
3
)
3
][BAr
F
4
] (
15
).
14
isomerizes to give
15
via
an 1,2-H shift reaction. Hydride addition to cation
3
gives a mixture of products [TbbGeHIrH(PMe
3
)
3
] (
16
) and [TbbGeIrH
2
(PMe
3
)
3
] (
17
) and a reversible 1,2-H shift between
16
and
17
was studied. In the tin case
4
the dihydride [TbbSnIrH
2
(PMe
3
)
3
] (
18
) was isolated exclusively. The PMe
3
and PEt
3
derivatives,
18
and [TbbSnIrH
2
(PEt
3
)
3
] (
19
), respectively, could also be synthesized in reaction of [TbbSnH
2
]
−
with the respective chloride [(R
3
P)
n
IrCl] (R = Me,
n
= 4; R = Et,
n
= 3). Reaction of complex
19
with CO gives the substitution product [TbbSnIrH
2
(CO)(PEt
3
)
2
] (
20
). Further reaction with CO results in hydrogen transfer from the iridium to the tin atom to give [TbbSnH
2
Ir(CO)
2
(PEt
3
)
2
] (
21
). The reversibility of this ligand induced reductive elimination transferring
20
to
21
is shown.
Tetrylidinium-iridium cations [ArE = IrHL
3
]
+
(E = Ge, Sn) show a vinyl-cation type bonding situation and are highly reactive electrophiles acting as a cooperative metal-ligand Lewis acid enabling 1,2-addition of NH
3
, N
2
H
4
, H
2
O, HCl and H
2
. |
|---|---|
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/d2sc05620h |