Reactivity of a β-diketiminate-supported magnesium alkyl complex toward small molecules

Article abstract of DOI:10.1039/c9dt00090a

The reactivity of the magnesium alkyl {[HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(ⁿBu)}₂ (1) toward various small molecules provides access to a variety of magnesium derivatives. For example, the insertion of elemental chalcogens (S₈ and Se₈) into the Mg-C bond of complex 1 gives the dimeric magnesium thiolate {[HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(μ-SⁿBu)}₂ (2), magnesium selenolate [HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(SeⁿBu)(THF) (3), and magnesium diselenolate [HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(Se₂ⁿBu)(THF) (4). Meanwhile, compound 4 can be readily obtained by further insertion of one selenium atom into complex 3. Moreover, the reactions of complex 1 with diphenyl dichalcogenides (PhSSPh and PhSeSePh) by σ bond metathesis afford the corresponding magnesium phenyl chalcogenolates [HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(EPh)(THF) (E = S 5, Se 6) concomitant with PhEⁿBu release. Furthermore, the treatment of complex 1 with benzonitrile and phenyl isothiocyanate produces the serendipitous magnesium-1-azaallyl complex [HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(N(H)C(Ph)CHC₃H₇)(DME) (7) and the diimino-thioamidato magnesium compound {κ³-N,N′,N′′-(ArNCMe)₂[N(Ph)CS]CH}Mg[(Ph)NC(ⁿBu)S] (8) (Ar = 2,6-ⁱPr₂C₆H₃). In addition, deprotonation occurs between compound 1 and 1-methylimidazole to generate the imidazolyl complex {[HC(C(Me)N-2,6-ⁱPr₂C₆H₃)₂]Mg(μ-Im)}₂ (9) (Im = 2-N-methylimidazolyl). These results indicated that the butylmagnesium complex 1 possesses high activity toward small molecules and revealed several unusual transformations. All the new compounds were characterized by various spectroscopic methods, and their solid-state structures were further confirmed by single-crystal X-ray diffraction analyses.

Full text of DOI:10.1039/c9dt00090a

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DOI: 10.1039/C9DT00090A
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Reactivity of a β-Diketiminate-Supported Magnesium Alkyl
toward Small Molecules†
Received 00th January 20xx,
Accepted 00th January 20xx
Wenshan Ren,* Shaohui Zhang, Ziyi Xu, Xuebing Ma*
Reactivity of the magnesium alkyl {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(nBu)}2 (1) toward various small molecules provides access
to a variety of magnesium derivatives. For example, elemental chalcogens (S8 and Se8) insert into the Mg-C bond of
complex 1 to give the dimeric magnesium thiolate {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(µ-SnBu)}2 (2), magnesium selenolate
[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SenBu)(THF) (3), and magnesium diselenolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(Se2nBu)(THF)
(4), respectively. Meanwhile, the compound 4 can be readily obtained by further insertion of one selenium atom into the
complex 3. Moreover, reactions of the complex 1 with diphenyl dichalcogenides (PhSSPh and PhSeSePh) by  bond
metathesis afford the corresponding magnesium phenyl chalcogenolates [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(EPh)(THF) (E = S 5,
Se 6) concomitant with the PhEnBu release. Furthermore, treatment of the complex 1 with benzonitrile and phenyl
DOI: 10.1039/x0xx00000x
www.rsc.org/
isothiocyanate
produces
the
serendipitous
magnesium-1-azaallyl
complex
[HC(C(Me)N-2,6-
iPr2C6H3)2]Mg(N(H)C(Ph)=CHC3H7)(DME) (7) and the diimino-thioamidato magnesium compound {κ3-N,N’,N’’-
(ArNCMe)2[N(Ph)CS]CH}Mg[(Ph)NC(nBu)S] (8) (Ar = 2,6-iPr2C6H3). In addition, deprotonation occurs between compound 1
and 1-methylimidazole to generate the imidazolyl complex {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(µ-Im)}2 (9) (Im
= 2-N-
methylimidazolyl). These results indicated that the butylmagnesium complex 1 possesses high activity toward small
molecules and reveals several unusual transformations. All the new compounds were characterized by various
spectroscopic methods, and their solid-state structures were further confirmed by single-crystal X-ray diffraction analyses.
trimesityldipyrromethene).3d,7 Besides these, the β-diketiminato
magnesium alkyl complexes8 have gained considerable recent
interest as catalysts in a variety of transformations, including
Introduction
Organomagnesium compounds are attractive to chemists due to
their spectacular reactivity and wide applications in innumerable
synthetic transformations. Among them, Grignard reagents1 are
undoubtedly the most important. However, a large amount of
studies have demonstrated that Grignard reagents exist in solution
as a complex mixture of species (e.g., the Schlenk equilibrium) and
exhibit various structures in solid state.2 These drawbacks
somewhat hamper deep investigations on the chemistry of the Mg–
R (R = a variety of hydrocarbyl groups) moiety of Grignard
compounds.3 Accordingly, various well-defined organomagnesium
derivatives have been prepared in the past three decades, and have
opened up a broad prospect for organomagnesiun chemistry.
Representative examples of this type include (Tp)MgR (Tp =
hydroboration of pyridines, imines, nitriles, isonitriles,
carbodiimides, aldehydes, and ketones;9 hydrodeoxygenation of
isocyanates;10 polymerization of alkenes;11 dehydrocoupling of
amines and boranes;12 ring-opening polymerization;3d,13 and
hydroamination of aminoalkenes.14 Moreover, these compounds
also show high reactivity toward a series of small molecules such as
white phosphorus,15 dioxygen,3d,16 N-heterocyclic molecules,17a
fluoroarenes,17b alcohols,8f amines,8f carboxylic acids,8f ketones,3d
and bis-pinacolatodiborane.18 Despite increasing interest in this
area, the investigation on the reactivity of β-diketiminate-
supported organomagnesium complexes is still in its infancy in
comparison with that of other alkylmagnesium compounds such as
(Tp)MgR3,4 and Grignard reagents.1 It was therefore of interest to
know if these species could possess other novel reactivity.
tris(pyrazolyl)borates),3a-c,4
(ToM)MgR
(Ar-BIAN)MgR
(ToM
(Ar-BIAN
=
=
phenyltris(oxazolinyl)borates),5
bis(arylimino)acenaphthenes),6 and (TMP)MgR (TMP
=
1,5,9-
Recently, our work has focused toward the development of the
chemistry of magnesium complexes.
A number of novel β-
diketiminato magnesium derivatives and unusual chemical
transformations have been described,19 which engendered our
continued interest in exploring the chemistry of other β-
College of Chemistry and Chemical Engineering, Southwest University, Chongqing
400715, China. E-mail: rwsh603@swu.edu.cn, zcj123@swu.edu.cn.
†Electronic Supplementary Information (ESI) available: Experimental procedures
and characterization data. CCDC numbers 1874067-1874072. Crystallographic
data collection, structure solution, refinement and X-ray diffraction details in CIF diketiminato magnesium compounds. Herein, we report the
format of compounds 2-4 and 7-9. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2019, 00, 1-3 | 1

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Ar
reactivity of a β-diketiminate-supported magnesium alkyl toward
small molecules such as elemental sulfur, elemental selenium,
diphenyl disulfide, diphenyl diselenide, phenyl isothiocyanate,
benzonitrile and 1-methylimidazole under mild conditions.
Ar
Ar
View Article Online
THF
DOI: 10.1039/C9DT00090A
nBu
nBu
N
N
N
N
N
PhEEPh
- PhEnBu
Mg
0.5
Mg
Ar
Mg
Ar
E
N
Ar
1
5
E = S ( )
Results and discussion
6
= Se ( )
Reactions of
1
with elemental chalcogens and phenyl
Scheme 2.
1
Reactions of complex with PhEEPh
chalcogenolates. Magnesium chalcogenolates have been proven to
play important roles in wide band gap semiconductors20a-d and
synthetic chemistry.20e,20f Therefore, the synthesis of these species
is of great interest. Treatment of the butylmagnesium complex
{[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(nBu)}2 (1)8f with two equivalents of
elemental sulfur or selenium in benzene (or benzene/THF) at room
temperature readily forms the magnesium thiolate {[HC(C(Me)N-
2,6-iPr2C6H3)2]Mg(µ-SnBu)}2 (2) and magnesium selenolate
characterized because of their instability; as a result, little is known
regarding their structures and properties.22a To the best of our
knowledge, compound
4
presents the first structurally
characteristic organomagnesium diselenolate, and the first example
of magnesium diselenolates obtained by direct insertion of two
selenium atoms into Mg-C bond.
Magnesium chalcogenolates can also be prepared from
metathesis reactions. The butylmagnesium complex {[HC(C(Me)N-
2,6-iPr2C6H3)2]Mg(nBu)}2 (1) reacts with diphenyl dichalcogenides
(PhSSPh and PhSeSePh) to give the corresponding magnesium
phenyl chalcogenolates [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(EPh)(THF) (E
= S 5, Se 6)19b concomitant with PhEC4H9 release (Scheme 2). These
reactions also demonstrate that the compound 1 can be employed
[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SenBu)(THF)
(3),
respectively
(Scheme 1). It should be noted that insertion reactions between
sulfur or selenium and Grignard reagents forming solutions
containing thiolate (-SR) or selenolate (-SeR) species have been well
documented,21 whereas the structures of the corresponding
products are not established by X-ray diffraction. The fully
characterized compounds 2 and 3 would aid in our understanding
of the structural features of these species as well as the insertion
processes between elemental chalcogens and Mg-C bond.
as
a useful reagent for preparation of the corresponding
asymmetric organochalcogenides.
The complexes 2-4 are stable in a dry nitrogen atmosphere,
while they are moisture sensitive. They have been characterized by
various spectroscopic techniques. In addition, the solid-state
structures of these complexes have been further confirmed by
single crystal X-ray diffraction analyses.
We also investigated the reaction of {[HC(C(Me)N-2,6-
iPr2C6H3)2]Mg(nBu)}2 (1) with elemental sulfur or selenium in 1:4
molar ratio. Unfortunately, treatment of the compound 1 with four
equivalents of sulfur does not give a desired magnesium dithiolate;
instead, a multi-component oily mixture is produced which is
unable to be identified. In contrast, we found that the expected
Fig. 1 depicts the molecular structure of {[HC(C(Me)N-2,6-
iPr2C6H3)2]Mg(µ-SnBu)}2 (2) which reveals a centro-symmetric dimer.
magnesium
diselenolate
[HC(C(Me)N-2,6-
n
iPr2C6H3)2]Mg(Se2 Bu)(THF) (4) can be isolated from the reaction of
the magnesium alkyl {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(nBu)}2 (1) with
four equivalents of elemental selenium in 56% yield (Scheme 1). In
addition, the magnesium diselenolate 4 can also be prepared by
direct insertion of one selenium atom into the corresponding
magnesium selenolate 3 in 59% yield (Scheme 1). Organometallic
diselenolates (RSeSeM) are useful reagents in organoselenium
chemistry.22 However, organomagnesium diselenolates are difficult
to
be
isolated
and
subsequently
Ar
Ar
Ar
Ar
nBu
N
Mg
nBu
nBu
1
N
N
N
N
N
N
S
1/8 S8
benzene
0.5
Mg
Ar
Mg
Ar
Mg
nBu
0.5
S
N
Ar
Ar
benzene,
2
THF
benzene,
THF
1/8 Se8
1/4 Se8
Ar
THF
Mg
Ar
THF
Fig. 1 ORTEP representation of 2. Displacement ellipsolids are set to
30% probability. Hydrogen atoms are omitted for clarity. Selected
distances (Å) and angles (°): Mg(1)-N(1) 2.0420(13), Mg(1)-N(2)
2.0435(13), Mg(1)-S(1) 2.4424(6), S(1)-C(1) 1.8234(16), S(1)-Mg(1)-
S(1) 82.698(19), N(1)-Mg(1)-N(2) 95.28(5), C(1)-S(1)-Mg(1),
123.26(6).
N
N
1/8 Se8
nBu
Se
nBu
Mg
Se
benzene
N
N
Se
Ar
Ar
Ar = 2,6-iPr2C6H3
3
4
Scheme 1.
1
Reactions of with S8 and Se8
2 | J. Name., 2019, 00, 1-3
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ARTICLE
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DOI: 10.1039/C9DT00090A
O
Ar
O
N
Ar
H
CH2CH2CH3
N
Mg
Mg
N
N
H
N
N
1,3-hydrogen
migration
C4H9
Ar
Ar
7
A
benzene,
DME
PhCN
PhCN
Ar
Ar
N
Mg
Ar
nBu
nBu
N
N
N
N
S
N
PhNCS
nBu
Mg
0.5
Mg
Ar
N
Ph
Ar
Ar
B
1
benzene
Ar
2 PhNCS
PhNCS
Fig. 2 ORTEP representation of 3. Displacement ellipsolids are set to
30% probability. Hydrogen atoms are omitted for clarity. Selected
distances (Å) and angles (°): Mg(1)-Se(1) 2.4863(6), Mg(1)-O(1)
2.0447(14), Mg(1)-N(1) 2.0529(15), Mg(1)-N(2) 2.0481(15), C(1)-
Se(1) 1.982(2), N(2)-Mg(1)-N(1) 93.97(6), C(1)-Se(1)-Mg(1)
103.61(7).
N
Ph
S
S
N
nBu
Mg
H
N
N
Ph
Ar
8
Scheme 3.
1
Reactions of complex with PhCN and PhNCS
ligand, -coordinated to one Se atom of butylseleno (or
butyldiseleno) group and one O atom of THF in a severely distorted
tetrahedral geometry featuring bond angles ranging from 93.97(6)
to 125.92(5)° and from 93.85(8) to 132.60(7)° in 3 and 4
respectively. The Mg-Se distances of 2.4863(6) and 2.5158(10) Å in
3 and 4 respectively, are close to these found in [HC(C(Me)N-2,6-
The Mg atom shows a severely distorted tetrahedral geometry with
angles ranging from 82.698(19) to 127.03(4)°. The Mg(1)–S(1) bond
length of 2.4424(6) Å is close to that found in [(η5-C5H5)Mg(µ2-
StBu)(tBupy)]2 (2.492(1) to 2.505(1) Å),23a but slightly elongated
compared to that in Mg(SMes)2(Et2O)2 (2.382(2) and 2.392(2) Å)23b
and [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SPh)(THF) (2.3839 (9) Å).19b The
angle of C(1)-S(1)-Mg(1) (123.26(6)°) is larger than that found in
iPr2C6H3)2]Mg(SePh)(THF)
(2.4988(8)
Å)19b
and
Mg(SeMes)2(THF)2(2.526 (3) and 2.539(3) Å).23b The covalent Se−Se
single bond distance within the structure of compound 4
(2.3432(10) Å) is comparable to that of {[HC(C(Me)N-2,6-
iPr2C6H3)2]Ni}2(μ-Se2) (2.3304(6) Å)24 and {Yb(DippForm)2}2{Se2}
[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SPh)(THF)
(106.63(9)°)19b
and
Mg(SMes)2(Et2O)2 (116.6(1) and 117.1(1)°).23b These observations
may be attributed to the sterically encumbered β-diketoiminato
ligands.
(2.3747(4)
Å,
DippForm
=
N,Nʹ-bis(2,6-
diisopropylphenyl)formamidinate).25 The angle of C(1)-Se(1)-Mg(1)
The
ORTEP
diagrams
of
and
[HC(C(Me)N-2,6-
[HC(C(Me)N-2,6-
iPr2C6H3)2]Mg(SenBu)(THF)
(3)
of compound 3 (103.61(7)°) is similar to that of Mg(SeMes)2(THF)2
iPr2C6H3)2]Mg(Se2 Bu)(THF) (4) are shown in Fig. 2 and 3. The central
Mg atom is -bound to two N atoms of [HC(C(Me)N-2,6-iPr2C6H3)2]-
n
(100.7(2)
and
101.8(2)°)23b
and
[HC(C(Me)N-2,6-
Fig. 4 ORTEP representation of 7. Displacement ellipsolids are set to
30% probability. Hydrogen atoms are omitted for clarity. Selected
distances (Å) and angles (°): Mg(1)-N(1) 1.9670(12), Mg(1)-N(2)
2.0616(11), Mg(1)-N(3) 2.0578(11), Mg(1)-O(1) 2.0387(10), N(1)-
C(1) 1.3756(17), C(1)-C(8) 1.3514(19), N(2)-Mg(1)-N(3) 94.33(4),
N(1)-Mg(1)-O(1) 108.88(5), C(1)-N(1)-Mg(1) 139.34(10), N(1)-C(1)-
C(2) 115.02(11), C(8)-C(1)-N(1) 126.58(13), C(1)-C(8)-C(9)
125.18(13).
Fig. 3 ORTEP representation of 4. Displacement ellipsolids are set to
30% probability. Hydrogen atoms are omitted for clarity. Selected
distances (Å) and angles (°): Mg(1)-Se(1) 2.5158(10), Mg(1)···Se(2)
3.1439(14), Mg(1)-O(1) 2.052(2), Mg(1)-N(1) 2.062(2), Mg(1)-N(2)
2.045(2), Se(1)-Se(2) 2.3432(10), N(2)-Mg(1)-N(1) 93.85(8), Se(2)-
Se(1)-Mg(1) 80.55(5).
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generate the anionic vinylamino ligand [N(H)C(Ph)=CHC3H7)]−.27 1
H
View Article Online
DOI: 10.1039/C9DT00090A
NMR monitoring of the reaction in D6-benzene showed that the
colour of the solution immediately turned to greenish-yellow upon
1
addition of PhCN; and the H NMR signals of the reaction mixture
exhibited downfield shifts compared with 1 which may ascribe to
the coordination of PhCN. After keeping at room temperature for
0.5 h, the typical 1H NMR signal at 4.29 ppm attributed to CH unit of
the C(Ph)=CHC3H7 fragment was observed. Although reaction of
magnesium alkyl complexes with α-H-free nitriles readily gives the
insertion products,28 the intermediate A could not be detected by
1H NMR spectroscopy. Compound 7 represents the first example of
magnesium-1-azaallyl complexes obtained by reaction of an
organomagnesium complex with a nitrile.
Fig. 5 ORTEP representation of 8. Displacement ellipsolids are set to
30% probability. Hydrogen atoms are omitted for clarity. Selected
distances (Å) and angles (°): Mg(1)-N(1) 2.139(2), Mg(1)-N(2)
2.121(2), Mg(1)-N(3) 2.180(2), Mg(1)-N(4) 2.158(2), Mg(1)-S(1)
2.4856(10), Mg(1)···C(1) 2.676(3), N(1)-C(1) 1.300(3), S(1)-C(1)
1.734(3), N(2)-C(27) 1.312(3), N(4)-C(24) 1.282(3), N(3)-C(34)
1.279(3), S(2)-C(27) 1.689(2), N(4)-Mg(1)-N(3) 90.19(8), N(1)-Mg(1)-
S(1) 67.66(6), N(1)-C(1)-S(1) 116.6(2), N(2)-C(27)-S(2) 131.07(19).
We next investigated the reactivity of complex 1 with phenyl
isothiocyanate. The reaction of the alkylmagnesium [HC(C(Me)N-
2,6-iPr2C6H3)2]Mg(nBu) (1) with one equivalent of isothiocyanate in
benzene at room temperature does not stop at the formal Mg-C
insertion product29 [HC(C(Me)N-2,6-iPr2C6H3)2]Mg[(Ph)NC(nBu)S] (B)
(Scheme 3); instead, the diimino-thioamidato magnesium
compound
{κ3-N,N’,N’’-(MeCN-2,6-
iPr2C6H3)2[N(Ph)CS]CH}Mg[(Ph)NC(nBu)S] (8) (Scheme 3) is formed in
which the β-diketiminate ligand undergoes electrophilic attack at
the γ-carbon of the NCCCN ring. Therefore, the compound 8 was
prepared by reaction of complex 1 with two equivalent of
isothiocyanate. Despite nucleophilic bond-forming reactions
involving the γ-carbon of the β-diketiminate ligands have been
reported with other heteroallenes30 such as carbon dioxide, carbon
disulfide, diphenylketene, phenyl isocyanate and diazoacetate, the
nucleophilic attack has not previously been reported to occur
between the γ-carbon and isothiocyanates. In the 1H NMR spectrum
of complex 8, the characteristic C-H resonance of the
[(ArNCMe)2[N(Ph)CS]CH] fragment observed at δ = 6.15. The 13C
NMR spectrum of the CH in the [(ArNCMe)2[N(Ph)CS]CH] ring
displayed a resonance at δ = 79.47.
iPr2C6H3)2]Mg(SePh)(THF) (104.16(8)°).19b The angle of Se(2)-Se(1)-
Mg(1) of complex 4 is 80.55(5)°.
Reactions of 1 with benzonitrile and phenyl isothiocyanate.
Encouraged by the above results, we then tried to extend our
studies to reactions of the alkylmagnesium complex {[HC(C(Me)N-
2,6-iPr2C6H3)2]Mg(nBu)}2 (1) with unsaturated organic molecules.
Treatment of the alkylmagnesium 1 with PhCN in 1:2 molar ratio at
room temperature forms the serendipitous magnesium-1-azaallyl
complex [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(N(H)C(Ph)=CHC3H7)(DME)
(7) in 75% yield (Scheme 3), which was confirmed by various
spectroscopic and X-ray crystallographic analyses. In its 1H NMR
spectrum, the single peak at δ = 2.32 was attributed to the
resonance of NH unit, and a triplet peak at δ = 4.29 was assigned to
the resonance of CH unit in the C(Ph)=CHC3H7 fragment. The 13C
NMR signals at δ = 151.91 and δ = 91.67 were attributed to the
C(Ph)=CHC3H7 unit. In the crystal structure of 7 (Fig. 4), the C(1)-C(8)
bond length (1.3514(19) Å) reveals substantial double-bond
character. Moreover, the bond angles around C(1) and C(8) are
consistent with sp2 hybridization. The distance of C(1)−N(1)
(1.3756(17) Å) is between the C-N single and double bonds,
revealing the delocalization character of the negative charge of the
N atom. The Mg(1)-N(1) bond length of 1.9670(12) Å is comparable
to that of [HC(C(Me)N-2,6-iPr2C6H3)2]Mg[N(SiMe3)2] (1.961(2) Å ),8f
[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(TMP) (1.9417(13) Å, TMP = 2,2,6,6-
tetramethylpiperidide)17a and [TismPriBenz]Mg[N(H)Ph](2.049(4) Å,
The molecular structure of 8 can be found in Fig. 5. The Mg
atom is -bound to one S atom and N atom of [(Ph)NC(nBu)S]-, -
coordinated to three N atoms of {(ArNCMe)2[N(Ph)CS]CH}- in a
distorted square pyramidal geometry. The bond angels of N(1)-
Mg(1)-N(3) and N(2)-Mg(1)-S(1) are 159.26(9) and 142.11(7)°,
respectively. The four membered ring Mg(1)-S(1)-C(1)-N(1) is almost
a planar structure with a torsion angle of 2.31°. The S(1)-C(1) and
C(1)-N(1) bond lengths, 1.734(3) and 1.300(3) Å respectively, are
between single and double-bond values (C-S 1.81 and 1.61, C-N
1.51 and 1.26 Å),31 which indicates delocalization of the negative
charge over the NCS unit. The backbone C(24)-N(4) and C(34)-N(3)
of the tripodal ligand, 1.282(3) and 1.279(3) Å respectively, are
consistent with double bonds, which are similar to those found in
{[κ3-N,N’,O-(DipNCMe)2(OCCPh2)CH]Mg(µ-I)}2 (1.283 Å)32 and [κ3-
N,N’,O-(MesNCMe)2(OCCPh2)CH]MgI(OEt2) (1.280 Å).32 The lengths
of the C(27)-S(2) and C(27)-N(2) bonds (1.689(2) and 1.312(3) Å,
respectively) are between the C-S and C-N single and double
bonds.31 The Mg(1)-N(2) bond length of 2.122(2) Å is longer than
that found in 7 (Mg(1)-N(1), 1.9670(12) Å). These observations also
suggest the delocalization of the negative charge over the NCS unit.
TismPriBenz
=
tris[(1-isopropylbenzimidazol-2-yl)-
dimethylsilyl)]methyl).26 These structural data indicate the
N(H)C(Ph)=CHC3H7 ligand is anionic.
A plausible reaction mechanism for 7 formation involves an
insertion of cyano group into the Mg−C σ bond of the complex 1 to
form
an
intermediate
compound
[HC(C(Me)N-2,6-
iPr2C6H3)2]Mg[N=C(Ph)C4H9)] (A) (Scheme 3), then the
[N=C(Ph)C4H9)]− moiety undergoes a 1,3-hydrogen migration to
4 | J. Name., 2019, 00, 1-3
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ARTICLE
Me
Ar
neutral nitrogen donors such as pyridine [HC(C(Me)N-2,6-
H
View Article Online
N
Ar
Ar
Ar
iPr2C6H3)2]Mg(Bu)(pyridine) (2.174(3) Å)33a and [HC(C(Me)N-2,6-
DOI: 10.1039/C9DT00090A
Me
nBu
nBu
N
N
N
N
N
N
N
N
N
N
N
iPr2C6H3)2]Mg(C12H13N2O2) (2.129(2) Å),33b or picoline [HC(C(Me)N-
2,6-iPr2C6H3)2]Mg(Bu)(2-picoline) (2.216(4) Å).34 While the Mg(1)-
C(1) distance of 2.1857(12) Å is slightly elongated compared with
that in aryl compound [[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(Ph)(OEt2)]
(2.139(3) Å).8f However, the Mg(1)–N(3) (2.0586(11) Å) and Mg(1)-
C(1) (2.1857(12) Å) distances are close to those witnessed in
Mg
Ar
Mg
Ar
Mg
Mg
THF, 60 o
C
N
Ar
Ar
Me
N
9
1
Scheme 4.
1
Reactions of complex with N-methylimidazole
Reaction of 1 with N-methylimidazole. Reaction of the compound {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(C3H4N3)}2 (Mg-Ntriazolyl, 2.075 Å; Mg-
1 with N-methylimidazole in THF is accompanied by elimination of Ctriazolyl, 2.195 Å).17b These results may be ascribed to some degree
the butane and the formation of the corresponding magnesium of delocalization of the negative charge over the N atom.17b
dimer {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(µ-Im)}2 (9) (Im
= 2-N-
methylimidazolyl) as shown in Scheme 4. In its 13C NMR spectrum, a
Conclusions
typical signal at δ = 185.4 ppm was assigned to the C-Mg resonance
from 2-N-methylimidazolyl ligand. While Hevia previously reported In conclusion, the reactivity of the β-diketiminate-supported
that the complex [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(nBu)(THF) is unable magnesium alkyl {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(nBu)}2 (1) toward
to promote the direct magnesiation of N-methylbenzimidazole at small molecules has been investigated, which provides access to a
the C2 position through deprotonation process,17a which may be variety of other magnesium derivatives and reveals several unusual
attributed to enhanced steric hindrance between the more bulky transformations. For example, complex 1 reacts with elemental
benzimidazole and the β-diketiminate ligand.
chalcogens and diphenyldichalcogenides to give a series of the
magnesium chalcogenolate complexes. Among them, the
The molecular structure of complex 9 is depicted in Fig. 6.
Although the structure of the magnesiation of the N-methyl
benzimidazole has been reported, the structural analysis was
complicated by disordered solvent molecules and by generally weak
diffraction.17a Hence, the molecular structure of 9 will further aid
the understanding of the structural features of such species.
magnesium
diselenolate
[HC(C(Me)N-2,6-
iPr2C6H3)2]Mg(Se2 Bu)(THF) (4) presents the first well characterized
organomagnesium diselenolate, and the first example of the
magnesium diselenolates obtained by direct insertion of two
selenium atoms into Mg-C bond. Meanwhile, the transformation
from a magnesium selenolate to corresponding diselenolate has
been directly proved by further insertion of one selenium atom into
the compound [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SenBu)(THF) (3).
Moreover, the reaction of magnesium alkyl 1 with benzonitrile
generate the first well defined magnesium-1-azaallyl complex
n
Similarly to the magnesiation of the N-methyl benzimidazole
by the [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(TMP) (TMP
= 2,2,6,6-
tetramethylpiperidide),17a the structure of 9 shows a centro-
symmetric dimer (Fig. 6) in which the two [HC(C(Me)N-2,6-
iPr2C6H3)2]Mg fragments are connected by two bridging imidazolyl
anions, generating a novel six-membered [MgCNMgCN] ring. Each
of the Mg atoms shows a severely distorted tetrahedral geometry,
with bond angles ranging from 91.42(4) to 117.99(4)°. The Mg(1)–
N(3) bond length of 2.0586(11) Å is shorter than those reported for
related β-diketiminate-supported magnesium compounds with
[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(N(H)C(Ph)=CHC3H7)(DME)
(7),
revealing an uncommon 1,3-hydrogen migration process.
Furthermore, the formation of the “tripodal” magnesium
compound {κ3-N,N’,N’’-(ArNCMe)2[N(Ph)CS]CH}Mg[(Ph)NC(nBu)S]
(8) indicates that the reaction of compound 1 with isothiocyanate
does not stop at the formal Mg-C insertion step, and the β-
diketiminate ligand further undergoes electrophilic attack at the γ-
carbon of the NCCCN ring. In addition, the alklymagnesium
compound 1 can react with N-methylimidazole via a deprotonation
process, eventually releasing the corresponding imidazolyl
derivative {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(µ-Im)}2 (9). Further
studies on organoalkaline-earth metal chemistry are ongoing and
the results will be reported in due course.
Conflicts of interest
There are no conflict to declare.
Acknowledgements
Fig. 6 ORTEP representation of 9. Displacement ellipsolids are set to
30% probability. Hydrogen atoms are omitted for clarity. Selected
distances (Å) and angles (°): Mg(1)-N(1) 2.0838(10), Mg(1)-N(2)
2.0695(10), Mg(1)-N(3) 2.0586(11), Mg(1)-C(1) 2.1857(12), N(2)-
Mg(1)-N(1) 91.42(4), N(3)-Mg(1)-C(1) 107.95(4).
This work was supported by the National Natural Science
Foundation of China (Grant No. 21772159, 21302155), and the
National Training Programs of Innovation and Entrepreneurship for
Undergraduates (Grant No. 201810635059).
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Journal Name
(e) V. Balasanthiran, M. H. Chisholm, K. Choojun, C. B. Durr
Notes and references
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View Article Online
DOI: 10.1039/C9DT00090A
O
Ar
Ar
H
O
N
CH2CH2CH3
N
N
PhCN
nBu
Mg
Mg
N
H
N
Ar
Ar
The reactivity of the butylmagnesium complex toward various small molecules has been investigated.