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B-substituted group 1 phosphides: synthesis and reactivity
1-Boryl-8-phosphinonaphthalenes 1-BCy 2 -8-PCl 2 -C 10 H 6 ( 1 ) and 1-BCy 2 -8-PPhCl-C 10 H 6 ( 2 ) were prepared and used as starting materials for the synthesis of B-substituted phosphides. The reduction of 1 and 2 by Mg provided neutral compounds [1-BCy-8-PCy-C 10 H 6 ] 2 ( 3 ) and [1-BCy 2 -8-P...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2023-11, Vol.52 (45), p.1687-16885 |
|---|---|
| Main Authors: | , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites |
| Online Access: | Get full text |
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| Summary: | 1-Boryl-8-phosphinonaphthalenes 1-BCy
2
-8-PCl
2
-C
10
H
6
(
1
) and 1-BCy
2
-8-PPhCl-C
10
H
6
(
2
) were prepared and used as starting materials for the synthesis of B-substituted phosphides. The reduction of
1
and
2
by Mg provided neutral compounds [1-BCy-8-PCy-C
10
H
6
]
2
(
3
) and [1-BCy
2
-8-PPh-C
10
H
6
]
2
(
4
). Compound
3
represents the dimer of phosphinoborane 1-BCy-8-PCy-C
10
H
6
while complex
4
is a rare example of a discrete B ← P coordinated diphosphine. The reduction of
2
by Na or K in THF yielded B-substituted group 1 phosphides [Na(THF)
3
]
+
[1-BCy
2
-8-PPh-C
10
H
6
]
−
(
5
) and {[K(THF)
2
]
+
[1-BCy
2
-8-PPh-C
10
H
6
]
−
}
∞
(
6
), which structurally resembled bulky group 1 phosphides. Complex
5
showed easy activation of elemental chalcogens E (E = O, S, Se) to give B-substituted chalcogenophosphinites {[Na(THF)
2
]
+
[1-BCy
2
-8-P(E)Ph-C
10
H
6
]}
2
(E = O (
7
), S (
8
), Se (
9
)) as the products of chalcogen insertion into the P-Na bond. Importantly no oxidation to dichalcogenophosphinates was observed. Compound
5
is tolerant of the C&z.dbd;O polar bonds in organic substrates and the reactions of
5
with 2,3-butanedione or an acyl chloride provided {[Na(THF)
2
]
+
[1-BCy
2
-8-P{CH&z.dbd;C(O)C(Me)O}Ph-C
10
H
6
]
−
}
2
(
10
) and [1-BCy
2
-8-P{C(O)
t
Bu}Ph-C
10
H
6
] (
11
). Finally, B-coordinated phosphatetrylenes [1-BCy
2
-8-P(SnL)Ph-C
10
H
6
] (
12
) and [1-BCy
2
-8-P(PbL)Ph-C
10
H
6
] (
13
) (L is {2,6-(Me
2
NCH
2
)C
6
H
3
}
−
) were also prepared by substitution reactions of
5
.
B-substituted group 1 phosphides were prepared. They showed interesting reactivity with elemental chalcogens E (E = O, S, Se), organic substrates and organometallic halides. |
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| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d3dt02568c |