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From M to M, M and M molecular alloy Pt-Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters
Ist Teil von
Dalton transactions : an international journal of inorganic chemistry, 2023-03, Vol.52 (12), p.3623-3642
Erscheinungsjahr
2023
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Heterometallic Chini-type clusters [Pt
6−
x
Ni
x
(CO)
12
]
2−
(
x
= 0-6) were obtained by reactions of [Pt
6
(CO)
12
]
2−
with Ni-clusters such as [Ni
6
(CO)
12
]
2−
, [Ni
9
(CO)
18
]
2−
and [H
2
Ni
12
(CO)
21
]
2−
, or from [Pt
9
(CO)
18
]
2−
and [Ni
6
(CO)
12
]
2−
. The Pt/Ni composition of [Pt
6−
x
Ni
x
(CO)
12
]
2−
(
x
= 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt
9
(CO)
18
]
2−
with [Ni
9
(CO)
18
]
2−
and [H
2
Ni
12
(CO)
21
]
2−
, as well as reactions of [Pt
12
(CO)
24
]
2−
with [Ni
6
(CO)
12
]
2−
, [Ni
9
(CO)
18
]
2−
and [H
2
Ni
12
(CO)
21
]
2−
, afforded [Pt
9−
x
Ni
x
(CO)
18
]
2−
(
x
= 0-9) species. [Pt
6−
x
Ni
x
(CO)
12
]
2−
(
x
= 1-5) were converted into [Pt
12−
x
Ni
x
(CO)
21
]
4−
(
x
= 2-10) upon heating in CH
3
CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt
12−
x
Ni
x
(CO)
21
]
4−
(
x
8) with HBF
4
·Et
2
O afforded the [HPt
14+
x
Ni
24−
x
(CO)
44
]
5−
(
x
0.7) nanocluster. Finally, [Pt
19−
x
Ni
x
(CO)
22
]
4−
(
x
= 2-6) could be obtained by heating [Pt
9−
x
Ni
x
(CO)
18
]
2−
(
x
= 1-3) in CH
3
CN at 80 °C, or [Pt
6−
x
Ni
x
(CO)
12
]
2−
(2-4) in DMSO at 130 °C. The molecular structures of these new alloy nanoclusters have been determined by single crystal X-ray diffraction. The site preference of Pt and Ni within their metal cages has been computationally investigated. The electrochemical and IR spectroelectrochemical behavior of [Pt
19−
x
Ni
x
(CO)
22
]
4−
(
x
= 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt
19
(CO)
22
]
4−
.
Molecular alloy Pt-Ni nanoclusters of increasing sizes were synthesized, their structures determined by X-ray crystallography, Pt-Ni distribution computationally investigated, and the effect of Pt-Ni replacement electrochemically studied.
Sprache
–
Identifikatoren
ISSN: 1477-9226
eISSN: 1477-9234
DOI: 10.1039/d2dt03607j
Titel-ID: cdi_rsc_primary_d2dt03607j
Format
–
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