Metal exchange in lithiocuprates: implications for our understanding of structure and reactivity† †Electronic supplementary information (ESI) available. CCDC 1540280–1540286. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01423f Click here for additional data file. Click here for additional data file
A new class of lithium cyanatocuprates are elucidated whose structures reveal a preference by copper for lower order structure formation. New reagents have been sought for directed ortho cupration in which the use of cyanide reagents is eliminated. CuOCN reacts with excess TMPLi (TMP = 2,2,6,6-tetra...
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Published in | Chemical science (Cambridge) Vol. 8; no. 7; pp. 4904 - 4916 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
Royal Society of Chemistry
04.05.2017
|
Subjects | |
Online Access | Get full text |
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Summary: | A new class of lithium cyanatocuprates are elucidated whose structures reveal a preference by copper for lower order structure formation.
New reagents have been sought for directed
ortho
cupration in which the use of cyanide reagents is eliminated. CuOCN reacts with excess TMPLi (TMP = 2,2,6,6-tetramethylpiperidide) in the presence of limited donor solvent to give crystals that are best represented as (TMP)
2
Cu
0.1
Li
0.9
(OCN)Li
2
(THF)
8
, whereby both Lipshutz-type lithiocuprate (TMP)
2
Cu(OCN)Li
2
(THF)
8a
and trinuclear (TMP)
2
(OCN)Li
3
(THF)
8b
are expressed. Treatment of a hydrocarbon solution of TMP
2
CuLi
9a
with LiOCN and THF gives pure
8a
. Meanwhile, formation of
8b
is systematized by reacting (TMPH
2
)OCN
10
with TMPH and
n
BuLi to give (TMP)
2
(OCN)Li
3
(THF)
2
11
. Important to the attribution of lower/higher order bonding in lithiocuprate chemistry is the observation that in crystalline
8
, amide-bridging Cu and Li demonstrate clear preferences for di- and tricoordination, respectively. A large excess of Lewis base gives an 8-membered metallacycle that retains metal disorder and analyses as (TMP)
2
Cu
1.35
Li
0.65
9
in the solid state. NMR spectroscopy identifies
9
as a mixture of (TMP)
2
CuLi
9a
and other copper-rich species. Crystals from which the structure of
8
was obtained dissolve to yield evidence for
8b
coexisting in solution with
in situ
-generated
9a
,
11
and a kinetic variant on
9a
(
i
-9a
), that is best viewed as an agglomerate of TMPLi and TMPCu. Moving to the use of DALi (DA = diisopropylamide), (DA)
2
Cu
0.09
Li
0.91
(Br)Li
2
(TMEDA)
2
12
(TMEDA =
N
,
N
,
N
′,
N
′-tetremethylethylenediamine) is isolated, wherein (DA)
2
Cu(Br)Li
2
(TMEDA)
2
12a
exhibits lower-order Cu coordination. The preparation of (DA)
2
Li(Br)Li
2
(TMEDA)
2
12b
was systematized using (DAH
2
)Br, DAH and
n
BuLi. Lastly, metal disorder is avoided in the 2 : 1 lithium amide : Lipshutz-type monomer adduct (DA)
4
Cu(OCN)Li
4
(TMEDA)
2
13
. |
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ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/c7sc01423f |