Group 13 metal carbochalcogenoato complexes: Synthesis, X-ray structure analysis, and reactions

Article abstract of DOI:10.1002/hc.21445

A series of alkali metal tetrakis(carbochalcogenoato)-gallates and -indates M[M′(EOCR)₄](solv.) (M?=?alkali metal; M′?=?Ga, In; E?=?S, Se) and tris(carbodithioato)aluminum, -gallates and -indates M′ (SSCR)₃ (M′?=?Al, Ga, In) were prepared by the reactions of alkali metal carbochalcogenate with metal trihalogenides (M′X₃; M′?=?Al, Ga, In; X?=?Cl, Br) and by those of piperidinium carbodithioates or carbodithioic and carboselenoic acids with M′X₃, respectively. An X-ray molecular structure analysis revealed that they have an acetone molecule as a crystal solvent. The reactions of the potassium complexes K[M′ (EOCR)₄](H₂O) (E?=?S, Se) with methanol and primary and secondary amines gave the corresponding methyl ester and amides in good yields, while the reactions with iodomethane and iodine gave S- and Se-methyl chalcogenoesters RCOEMe (E?=?S, Se) in good yields. Similar reactions of the tris(carbodithioato)gallates and -indates led to the corresponding O-methyl thioesters, thioamides, and S-methyl dithioesters in moderate to good yields. Oxidation of the tetrakis- and tris-derivatives with iodine afforded the corresponding diacyl dichalcogenides (RCOE)₂ (E?=?S, Se) and di(carbothioyl) disulfides in quantitative yields. These reactions appeared to occur on the carbonyl or selenium atom of the tetrakis compounds and on the sulfide sulfur or thiocarbonyl carbon atom of the tris-compounds, respectively. A possible mechanism for these I₂-oxidation reactions is discussed.

Full text of DOI:10.1002/hc.21445

Received: 12 September 2018
DOI: 10.1002/hc.21445
Revised: 8 October 2018
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R E S E A R C H A R T I C L E
Group 13 metal carbochalcogenoato complexes: Synthesis, X-ray
structure analysis, and reactions
Norio Nakata1
Shinzi Kato1,2
Osamu Niyomura2
Masahiro Ebihara1
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1Department of Chemistry and Biomolecular
Science, Faculty of Engineering, Gifu
University, Gifu, Japan
2Department of Applied Chemistry, College
of Engineering, Chubu University, Kasugai,
Aichi, Japan
Abstract
A series of alkali metal tetrakis(carbochalcogenoato)-gallates and -indates
M[M′(EOCR)4](solv.) (M = alkali metal; M′ = Ga, In; E = S, Se) and
tris(carbodithioato)aluminum, -gallates and -indates M′ (SSCR)3 (M′ = Al, Ga, In)
were prepared by the reactions of alkali metal carbochalcogenate with metal trihalo-
genides (M′X3; M′ = Al, Ga, In; X = Cl, Br) and by those of piperidinium carbodith-
ioates or carbodithioic and carboselenoic acids with M′X3, respectively. An X-ray
molecular structure analysis revealed that they have an acetone molecule as a crystal
solvent. The reactions of the potassium complexes K[M′ (EOCR)4](H2O) (E = S,
Se) with methanol and primary and secondary amines gave the corresponding methyl
ester and amides in good yields, while the reactions with iodomethane and iodine
gave S- and Se-methyl chalcogenoesters RCOEMe (E = S, Se) in good yields.
Similar reactions of the tris(carbodithioato)gallates and -indates led to the corre-
sponding O-methyl thioesters, thioamides, and S-methyl dithioesters in moderate to
good yields. Oxidation of the tetrakis- and tris-derivatives with iodine afforded the
corresponding diacyl dichalcogenides (RCOE)2 (E = S, Se) and di(carbothioyl) di-
sulfides in quantitative yields. These reactions appeared to occur on the carbonyl or
selenium atom of the tetrakis compounds and on the sulfide sulfur or thiocarbonyl
carbon atom of the tris-compounds, respectively. A possible mechanism for these
I2-oxidation reactions is discussed.
Correspondence
Shinzi Kato, Department of Applied
Chemistry, College of Engineering, Chubu
University, Naka-ku, Nagoya, Japan.
Email: kshinzi@nifty.com
and
Masashiro Ebihara, Department of
Chemistry and Biomolecular Science,
Faculty of Engineering, Gifu University,
Gifu, Japan.
Email: ebihara@gifu-u.ac.jp
in metal-organic chemical vapor deposition (MOCVD).[4]
In contrast, little is known about the related carbo-thioato,
1
INTRODUCTION
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The chemistry of metal-sulfur and -selenium bonds has at-
tracted considerable attention over the past three decades
due to their chemical and physical properties[1] as well
as from a biochemical perspective.[2] Among the sulfur li-
gands, dithiocarbamate (RR’NCSS) derivatives containing
a Group 13 element have been extensively studied in great
detail[3], and it has been shown that tris-bidentate complexes
-selenoato, and -dithioato Group 13 metal complexes, most
likely due to the difficulty of their preparation and purifica-
tion. To the best our knowledge, almost nothing is known
about aluminum and gallium carbochalcogenoato complexes
except for two boron and indium complexes: [(9-BBN)
SSCPh][5] and [In(SSCCH2Ph)3],[6] respectively. We previ-
ously reported the synthesis and structural analysis of a series
of alkali metal carbochalcogenoate and Group 14-16 element
derivatives.[7,8] These successful results inspired us to study
the synthesis and structural analysis of gallium and indium
complexes with carbo-thioato, -dithioato-, and -selenoato li-
gands. As a part of our studies concerning carbochalcogenoic
acid derivatives, we report here the synthesis, structure, and
[3]
M(SSCNRR’)3 can serve as molecular precursors for use
Dedicated to Prof. Naomichi Furukawa on his 81th birthday.
Contract grant sponsor: Scientific Research on Priority Areas
Contract grant sponsor: Scientific Research from the Ministry of Education,
Science, Sports and Culture of Japan
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Heteroatom Chemistry. 2018;e21445.
https://doi.org/10.1002/hc.21445
wileyonlinelibrary.com/journal/hc
© 2018 Wiley Periodicals, Inc.
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TABLE 1 Yields of potassium tetrakis(carbochalcogenoato)gallates 3, 4 and -indates 5, 6
K[Ga(EOCR)4]
R
K[In(EOCR)4]
R
No.
E
Yielda (%) Mpb (°C) Color
No.
E
Yielda (%) Mpb (°C) Color
3a
3b
3c
3d
3e
3f
4a
4b
4c
4d
4e
4f
tert-C4H9
C6H5
S
S
S
S
S
S
Se
86 (22)
82 (24)
82 (17)
87 (27)
92 (28)
92 (29)
87(23)
181-186
184-187
200-204
171-175
168-173
152-156
180-184
179-183
145-148
167-173
132-137
173-176
colorless
colorless
colorless
colorless
colorless
colorless
colorless
colorless
colorless
colorless
5a
5b
5c
5d
5e
5f
6a
6b
6c
6d
tert-C4H9
C6H5
S
S
S
S
S
S
Se
Se
Se
83 (22) 190-195
98 (31) 171-176
82 (17) 209-214
84 (27) 161-166
94 (42) 171-176
93 (24) 141-144
96 (26) 179-182
88 (49) 189-192
85 (30) 129-135
88 (21) 148-152
81 (30) 171-176
90 (27) 141-144
Colorless
Colorless
Pale yellow
Colorless
Colorless
Colorless
Colorless
Colorless
Colorless
Colorless
Pale yellow
Colorless
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
4-ClC6H4
tert-C4H9
C6H5
4-CH3C6H4
2-CH3OC6H4 Se 90 (36)
4-CH3OC6H4 Se 94 (25)
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
4-ClC6H4
tert-C4H9
C6H5
4-CH3C6H4
2-CH3OC6H4 Se
4-CH3OC6H4 Se
Se 92 (30)
Se 97 (55)
pale yellow 6e
colorless 6f
4-ClC6H4
Se 92 (33)
4-ClC6H4
Se
aThe value in parenthesis represents isolated yield.
bDecomposition; micro crystals.
reactions of tris- (carbochalcogenoato)aluminum, -gallium,
and -indium complexes. During our study of Group 13 el-
ement derivatives with carbochalcogenoate ligands,[9]
we have found papers by Nöth et al.[10][HL(In(SOCMe)4
2
RESULTS AND DISCUSSION
Syntheses
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2.1
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(HL = 3,5-dimethylpyridinium)], Shang et al.[11]
, Vittal
Initially, the reaction conditions for potassium
4-methylbenzenecarbothioate 1c and -selenoate 2c with
GaBr3 and InCl3 were examined in detail. The reactions of
three equivalents of 1c or 2c with GaBr3 and InCl3 in water
proceeded smoothly at room temperature to give the corre-
sponding potassium tetrakis(carbochalcogenoato)gallates 3c
and 4c and -indates 5c and 6c as colorless micro crystals.
Under similar conditions, the reactions using other potassium
carbochalcogenoates 1 or 2 led to the corresponding tetrakis-
derivatives 3-6 in good yields as colorless to pale yellow
micro crystals (Scheme 1, Table 1). The reactions of other
alkali metal or tetramethylammonium carbochalcogenoates
with InCl3 gave the corresponding metal tetrakis-derivatives
M[In(EOCR)4](solv.) (M = Li, Na, Rb, Cs, Me4N; E = S,
Se), 7 and 8. (Scheme 2, Table 2). In these reactions, the for-
mation of tris(carbochalcogenoato) derivatives M(RCOE)3
(M = Ga, In; E = S, Se) was not detected under various
conditions.
et al.[12] (Et3NH[M(EOCPh)4] (M = Ga, In, E = S, Se), and
Ziemkowska et al.[13] (Et3NH[In(EOCPh)4] (E = S, Se) and
Ga(SOCPh)3), respectively.
In contrast to the reactions of alkali metal carbochal-
cogenoates 1 and 2, those of piperidinium carbodithioates
9 with GaCl3 and InCl3 proceeded quickly in CH2Cl2 at
room temperature to give the expected tris(carbodith-
ioato)gallium 10 and -indium 11 in quantitative yields
as orange crystalline solids (Scheme 3, Table 3). In
the reactions of MCl3 (M = Ga, In) with piperidinium
4-methylbenzenecarbodithioate 9d in molar ratios of 1:1
and 1:2, the expected dichloro [MCl2(SSCC6H4(4-Me))]
and monochloro derivatives [MCl(SSCC6H4(4-Me))2]
SCHEME 1 Syntheses of potassium tetrakis
(carbochalcogenoato) gallates 3 and 4, and -indates 5 and 6

NAKATA eT Al.
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with excess potassium arenecarbodithioates. Presumably,
the coordination of four carbodithioate groups to Group 13
metals may be prevented by such bidentate character of the
carbodithioato ligands.
The preparation of tris(carbodithioato)aluminums
Al(SSCR)3 was also investigated. The reactions of car-
bodithioic acids 12 instead of their piperidinium salts 9 with
trimethylaluminum in hexane gave the corresponding tris(-
carbodithioato)aluminums 13 as orange to yellow-orange
micro crystals. (Scheme 4, Table 4).
To the best of our knowledge, there has been no previous
report on the synthesis of carboselenoate aluminum, most
likely due to the difficulty of the preparation of pure car-
boselenoic acids and their alkali metal or ammonium salts.[14]
Previously, we developed convenient methods for the prepa-
ration of tris(arenecarbodithiolato)aluminum.[15] This suc-
cess inspired us to prepare tris(carboselenoato)aluminums.
SCHEME 2 Syntheses of alkali metal tetrakis
(carbochalcogenatoato)- indates 7 and 8
TABLE 2 Yields of alkali metal and
ammonium tetrakis(carbothioato) 7 and
-(carboselenoato)indates 8
M[In(RCOE)4]
No.
M
R
E
Yielda (%)
Color
7da
7db
7dc
7dd
7de
8dc
Li
4-MeC6H4
S
S
S
S
S
Se
7
89
35
47
49
78
mcb
Colorless
Pale yellow
Colorless
Colorless
Colorless
Yellow
Na
Rb
Cs
Me4N
Na
mc
Needles
Needles
Needles
mc
aIsolated yield.
bMicro crystals.
In fact, carboselenoic acids 14 readily react with Me3Al at
0°C to give the expected tris(carboselenoato)aluminums 15
in good yields (Scheme 5, Table 5).
The obtained sulfur derivatives 3 and 5 are stable around
room temperature in air and can be stored for more than 2 months
without any appreciable change. However, the selenium deriva-
tives gradually decomposed both in air and in solvent even in a
refrigerator (ca. −2°C) with a separation of red selenium.
The structures of these complexes 3-8, 10, 11, 13, and 15
were confirmed by IR and 1H, and 13C{1H} and or 77Se{1H}
NMR spectroscopy, elemental analysis, and X-ray molecular
structure analysis. Their IR and NMR spectral data are col-
lected in Tables S3-S6. In the IR spectra (KBr) of complexes
3-8, strong bands due to νC=O stretching frequencies were
observed in the range of 1605-1650 cm−1. In the 13C NMR
spectra, a characteristic peak is observed in the range of δ
198-217 (for the COE of compounds 3-8). On the other hand,
the νCSS stretching frequencies and 13CSS signals of com-
pounds 10 and 11 appear in the regions 950-1027 cm−1 and
δ 239-267, respectively. The 13COE (δ 214-217) and 13CSS
signals (δ 267-270) of the alkyl derivatives (3a, 4a, 5a, 6a,
SCHEME 3 Syntheses of tris(carbodithioato)gallium 10 and
-indium 11
were not detected. In addition, the expected tetrakis-
derivatives K[M(SSCR)4] (M = Ga, In; R = aryl) were not
detected from the reactions of trihalogallium and -indium

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TABLE 3 Yields of tris(carbodithioato)gallium 10 and -indium 11
Ga(SSCR)3
R
Mpb
In(SSCR)3
R
Yielda
(%)
No.
Yielda(%)
(°C)
Colorc
No.
Mpb (°C)
Colorc
10a
10b
10c
10d
10e
10f
iso-C4H9
C6H5
95 (77)
86 (35)
99 (68)
95 (52)
92 (33)
99 (54)
95 (36)
110-113
148-150
147-151
113-117
175-177
212-215
136-140
Yellow
Orange yellow
Orange
Orange
Brown
11a
11b
11c
11d
11e
11f
iso-C4H9
C6H5
78 (73)
77 (52)
92 (71)
89 (68)
89 (42)
91 (48)
93 (32)
121-125
151-153
147-151
124-128
193-196
171-174
142-144
Yellow
Orange yellow
Orange
Orange
Orange yellow
Orange
2-CH3C6H4
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
4-ClC6H4
2-CH3C6H4
4-CH3C6H4
2-CH3OC6H4
4-CH3OC6H4
4-ClC6H4
Brown
Brown
10 g
11 g
Orange
aThe value in parenthesis shows isolated yield.
bDecomposition.
cMicro crystals.
SCHEME 4 Syntheses of tris(carbodithioato)aluminum 13
TABLE 4 Yields of tris(carbodithioato)-aluminum 13
Al(SSCR)3
SCHEME 5 Syntheses of tris(carboselenoato)aluminums 15
No.
R
Yielda (%)
Color
13a
13b
13c
13d
13e
13f
C6H5
62
74
71
87
92
92
mcb
mc
mc
mc
mc
mc
Orange
Orange
Brown
Orange
Yellow
Orange
TABLE 5 Yields and physical properties of tris(carboselenoato)
aluminums 15
2-MeC6H4
4-MeC6H4
2-MeOC6H4
4-MeOC6H4
4-ClC6H4
Al(SeOCR)3
No.
R
Yielda (%)
Color
15a
15b
15c
15d
15e
4-MeC6H4
4-MeOC6H4
4-ClC6H4
2,4,6-(Me)3C6H4
1-Naph
61
89
84
75
79
mcb
mc
mc
mc
mc
Orange
Yellow
Yellow
Orange
Yellow
aIsolated yield.
bMicro crystals.
10a, and 11a) are shifted downfield compared to those [δ
198-203 (COE) and δ 241-253 (CSS)] of the aromatic deriv-
atives, respectively. These downfield shifts may result from
less π-conjugation of the alkyl groups to the COS, COSe, or
CSS moieties.
aIsolated yields.
bMicro crystals.
and by recrystallization from a variety of solvents. However,
these attempts were unsuccessful most likely due to their
strong hygroscopicity. As mentioned above, however, the
water molecules in these complexes may have been part of
a crystal water. In fact, an X-ray molecular structure analysis
revealed that 4-methylbenzene derivatives 3c, 4c, 5c, and 6c,
which were recrystallized from a variety of solvents: 3c was
recrystallized from a mixed solvent of tetrahydrofuran (THF)/
2.2
Crystal structures
|
In general, alkali and alkali-earth metal carbochalcogenoates
such as lithium and sodium salts M(EE′CR) (M = Li, Na;
E = S, Se; E′ = O, S) are hygroscopic and it is very difficult
to remove any water they contain.[7] We tried to remove a
small amount of water in 3-6 under high-vacuum conditions

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FIGURE 1 ORTEPs of A,
K[Ga(SOCC6H4(4-Me))4]·1.5(THF)
3c·1.5(THF), B, K[Ga(SeOCC6H4(4-
Me))4]·Me2CO 4c·Me2CO, C,
K[In(SOCC6H4(4-Me))4]·Me2CO
5c·Me2CO, D, K[In(SeOCC6H4(4-
Me))4]·Me2CO 6c·Me2CO, E,
Ga(SSCC6H4(2-Me))3 10c, and F,
In(SSCC6H4(2-Me))3 11c with 30%
probability. Hydrogen atoms are omitted for
clarity
hexane and contained 1.5 THF molecules {K[Ga(SOCC6H(4-
Me))4]·1.5(THF)}, while 4c, 5c, and 6c which were recrys-
tallized from a mixed solvent of acetone/dichloromethane/
hexane contained an acetone molecule {K[M(EOCR)4]
(Me2CO) (M = Ga, In; E = S, Se)}. In contrast, single crys-
tals of tris(2-methylbenzene-carbodithioato)gallium 10c and
-indium 11c, which were obtained by slow evaporation of a
concentrated mixed solution of acetone/hexane or hexane/ac-
etone/CH2Cl2 did not include any crystal solvent.
Figure 1A. The four carbothioate ligands coordinate to the
gallium center through the sulfur atom. The Ga–S distances
(2.273(3)-2.291(3) Å) are almost identical to the sum of their
covalent bond radii (2.29 Å)[17-19] The distances are similar to
those in the related complexes.[12d,12e] The geometry around
Ga atom is slightly distorted tetrahedron with one relatively
small [102.89(11)°] and one relatively wide [121.65(11)°]
S–Ga–S angles. The C–S [1.736(10)-1.786(10) Å] and C–O
bond distances [1.192(9)-1.224(9) Å] in the carbothioate
groups are C–S single (1.81 Å)[17] and C=O double bonds
(1.20 Å),[17] respectively. The anionic gallium complex co-
ordinates to potassium ion by two oxygen and one sulfur
atoms. The potassium ion is also coordinated by one oxygen
and one sulfur atom of the symmetry-related gallium com-
plex and one THF molecule. This coordination environment
made complex 3c polymeric chain along the b axis (Figure
S1). One more THF molecule located around an inversion
center (0, 1/2, 0) was disordered. This molecule coordinates
The ORTEPs of the compounds are shown in Figure 1 [16]
Their crystal data and selected bond lengths and angles: see
Supporting information, Tables S1 and S2, respectively.
2.2.1
K[Ga(SOCC6H4Me-4)4]·1.5(THF)
|
3c·1.5(THF)
Compound 3c·1.5(THF) was crystallized in the monoclinic
space group P21/n. The structure of 3c·1.5(THF) is shown in

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to one of two potassium ions that were related by the inver-
sion center (Figure S2). Therefore, a half of the potassium
ions in this structure are seven coordinated and the remaining
ones six coordinated and then 3c·1.5(THF) can be expressed
as [K(THF)1.5{Ga(SOCC6H4(4-Me))4}].
groups and two MeCN molecules. The K–O distances
[2.693(2)-2.797(4) Å] are slightly longer that those observed
in our structures [2.611(7)-2.687(7) Å]. The K–S [3.664(1)-
3.882(1) Å] and K–Se distances [3.750(1)-3.857(2) Å] are
also longer than the corresponding distances in our structures
[K–S 3.605(4)-3.730(4) Å and K–Se 3.6208(19)-3.7030(19)
Å]. The differences may be due to the small coordination
number, seven, of potassium in our structures.
2.2.2
K[M(XOCC6H4(4-Me))4]·Me2CO [(M
|
= Ga, X = Se) 4c· Me2CO; (M = In, X = S) 5c·
Me2CO; (M = In, X = Se) 6c· Me2CO]
2.2.3
Ga(SSCC6H4(2-Me))3 10c and
|
The structures of 4c·Me2CO, 5c·Me2CO, and 6c·Me2CO are
crystallized in the monoclinic space group P21/n and are iso-
structural (Figures 1B-D). In these structures, the gallium (or
indium) atom is coordinated by four carboselenoate (or car-
bothioate) groups through the selenium (or sulfur) atom. The
potassium ion is coordinated by one selenium (or sulfur) and
two oxygen atoms of the anionic gallium complex. The po-
tassium ion is also coordinated by one oxygen and two sele-
nium (or sulfur) atoms of the symmetry-related complex and
one acetone molecule. This coordination environment makes
the complexes polymeric chain along the b axis (The chain
structure of 4c·Me2CO is shown in Figure S3). This sug-
gests that the complexes should be expressed as [K(Me2CO)
{M(XOCC6H4(4-Me))4}].
In(SSCC6H4(2-Me)3 11c
The single crystals of compounds 10c and 11c were obtained
by crystallization from a mixed solvent of dichloromethane
and hexane. The structures of both compounds 10c and 11c
resemble each other (Figure 1E,F). These compounds exist
as monomers and without any crystal solvent. Three carbo-
dithioate groups are coordinated to the gallium and indium
centers in a bidentate fashion. The average C–S bond dis-
tances [1.689(2) Å for 10c and 1.692(2) Å for 11c] of the
three carbodithioate groups are roughly midway between
C–S single and C=S double bonds, respectively (C=S bond
distances of common dithioesters are 1.62−1.64 Å).[17]
The gallium complex 10c is the first example of a
structurally characterized tris(carbodithioato)gallium. The
Ga–S bonds [2.407(1)-2.464(1) Å] are longer than the sum
of their covalent bond radii (2.29 Å)[17], but close to those
of the tris(dithiocarbamato)-[3a,3b,3d] and tris(xanthato)gal-
lium complexes[20], for example, Ga(SSCNEt2)3 (ave. 2.436
Å)[3a] and Ga(SSCOEt)3 (ave. 2.435 Å)[20]. The In–S bond
distances [2.5792(12)–2.6258(13) Å] are slightly longer
than the sum of their covalent bond radii (2.54 Å),[16,17]
but close to those with S-donated bidentate ligands such
In 4c·Me2CO, the Ga–Se distances [2.3997(11)-
2.4173(12) Å] are almost identical to the sum (2.43 Å) of the
radius of Ga (1.26 Å) and the radius of Se (1.17 Å), indicat-
ing a Ga–Se covalent bond. In 5c·Me2CO and 6c·Me2CO, the
In–S [2.475(3)-2.498(3) Å] and In–Se [2.571(2)-2.5898(19)
Å] are nearly equal to the sum of their covalent radii (In–S
2.46 Å and In–Se 2.60 Å). These distances are similar to the
corresponding bond distances in the reported structures of
[M(XOCR)4]− (M, X = Ga, Se; [12g] In, S;[9,12c-12f] In, Se[12g]
.
The C–S or C–Se distances and C–O distances of these com-
plexes indicate that the C–S or C–Se is a single bond and the
C–O is a double bond.
In these complexes, MX4 (M = Ga, In; X= S, Se) is
a distorted tetrahedral geometry of which some X–M–X
angles much deviates from the ideal value. In particular,
S1–In1–S3 in 6c·Me2CO is the widest angle [131.15(9)°]
in all the structures. This wide angle may be accompanied
by short contact of oxygen with In atom [In1···O 2.762(7)
Å and In1···O3 2.830(7) Å] that are much smaller than the
sum of van der Waals radii (In···O 3.45 Å). Similar wide
angle of S–In–S with short contact of In···O is observed in
[(Ph3P)2AgIn(SCOPh)4][12a] and [Li{In(SOCPh)4}] ·0.25(H2
O)·0.5(MeCN).[12c]
The structures most closely related to 3c·1.5(THF),
4c·Me2CO,
5c·Me2CO,
and
6c·Me2CO
are
[K(MeCN)2{M(XC{O}Ph)4] (M, X = Ga, Se; In, S; In,
Se).[12g,12c] The structures of [K(MeCN)2{M(XC{O}Ph)4] are
also isostructural.[12c] The potassium is coordinated by three
oxygen and three chalcogen atoms of six carbochalcogenoate
SCHEME 6 Reactions of the 4-methyl derivatives 3c-6c with
various reagents

NAKATA eT Al.
7 of 10
|
TABLE 6 The reaction conditions of compounds 3-6 with methanol, amines, iodomethane, and iodine and the yields of products 16-21
Reaction condition
K[M(EOCR)4]
R
Reactant
Time
Solvent Temp. (°C) (h)
Yielda
M
E
Compd. no.
A
3-6/A
Products
(%)
4-CH3C6H4
Ga
In
Ga
S
S
S
3c
5c
3c
MeOH (excess)
MeOH
64
24
RCOOMe 16
68
39
52
CH2=CHCH2NH2
THF
25
1
RCONHCH2CH=CH2
17a
In
Ga
In
S
S
S
S
5c
3c
5c
3c
47
77
73
85
Et2NH
1/4
1/4
THF
THF
25
23
1
1
RCONEt2 17b
Ga
In
Ga
In
Ga
In
S
S
S
S
S
5c
3c
5c
3c
5c
89
32
28
94
85
75
86
-
MeI (excess)
1/4
MeI
42
25
64
25
1
24
1
RCOSMe 18
(RCOS)2 20
RCOOMe 16
I2 (excess)
THF
MeOH
THF
Ga Se 4c
In Se 6c
Ga Se 4c
MeOH (excess)
CH2=CHCH2NH2
1
RCONHCH2CH=CH2
17a
In Se 6c
Ga Se 4c
In Se 6c
Ga Se 4c
-
-
-
75
Et2NH
1/4
1/4
THF
THF
25
23
1
1
RCONEt2 17b
In Se 6c
Ga Se 4c
In Se 6c
Ga Se 4c
In Se 6c
74
51
43
95
90
MeI (excess)
I2 (excess)
1/4
MeI
42
25
24
24
RCOSeMe 19
(RCOSe)2 21
THF
aIsolated yields.
as carbodithioates,[6,21,22] dithiocarbamates,[3,22-29] and
xanthates,[20,30,31] for example, In(SSCCH2Ph)3 (ave. 2.603
Å),[6] In(SSCNEt2)3 (ave. 2.597 Å)[3a] and In(SSCOEt)3
(ave. 2.598 Å).[20] The dihedral angles between the ben-
zene rings containing C10 and C18 and the carbodithioate
planes in compound 10c were 49.11(8)° and 49.7(2)°, re-
spectively, while that of C2 was 23.20(17)°. In compound
11c, the angles between the benzene rings containing C10
and C18 and the carbodithioate planes were 54.25(10)° and
54.1(3)°, respectively, while that of C2 was 28.3(2)°. The
bonds around the Ga and In atoms are considered to adopt
trigonally distorted octahedral geometries (the trans angles
are 158.58(3)-166.28(3)° for 10c and 154.47(4)-163.01(4)°
for 11c). The intermolecular short contacts of 10c and 11c
see Figures S4 and S5, respectively. For their packings, see
Figure S6. Both (a) Packings of Ga(SSCC6H4(2-Me))3
10c and (b) In(SSCC6H4(2-Me))3 11c view down the
a-axis, respectively. Green, yellow and gray balls are gal-
lium or indium, sulfur and carbon atoms, respectively. All
hydrogen atoms are omitted for clarity. Structures 10c-A,
10c-A’, 10c-B and 10c-B’ in (a) and 11c-A, 11c-A’, 11c-B
and 11c-B’ in (b) are enantiomorphic, each other.
2.3
Reactions
|
The reactions of the 4-methyl derivatives of tetrakis-
(carbochalcogenoato)gallates 3, 4, and -indates 5, 6 with
alcohol, amines, iodomethane, and iodine were examined
(Scheme 6). The reaction conditions and yields are shown in
Table 6.
4-Methylbenzene derivatives (3c, 4c, 5c and 6c) do not
react with MeOH below 20°C. However, the reactions under

8 of 10
NAKATA eT Al.
|
refluxing methanol proceeded to give the corresponding
methyl esters 16 in good yields. On the other hand, the reac-
tions with primary and secondary amines proceeded at room
temperature to afford the corresponding amides 17 in 70%-
79% yields. Reflux of 3c, 4c, 5c and 6c in iodomethane gave
the corresponding S-methyl thioester 18 and Se-methyl selen-
oester 19 in good yields, respectively. Oxidation of 3c, 4c, 5c,
and 6c with iodine at room temperature for 1 h afforded di(4-
methylbenzoyl) disulfide 20 and diselenide 21 in quantitative
yields, respectively.
On the other hand, the reactions of tris(4-methylbenzene-
carbodithioato)gallium 10d and -indium 11d with alcohol,
amines, iodomethane and iodine were examined (Scheme 7).
The reaction conditions and products are shown in Table 7.
These results clearly indicate that compounds 10d
and 11d react differently with the corresponding alkali
metal salts M(RCSS) (M = Li, Na, K, Rb, and Cs), which
show relatively high ionic properties.[14] Diacyl dichalco-
genides.[32] 20, 21 and di(thioacyl) disulfide 25 may be
formed via acylchalcogenyl iodide[33] 26 (E = O, E′ = S,
Se) or thioacylsulfenyl iodides[34] 26 (E, E′ = S) and their
radical 27 (Scheme 8).
3
CONCLUSIONS
|
The reactions of alkali metal carbothioates and carbose-
lenoates with Group 13 metal trihalides [MX3 (M = Ga,
In; X = Cl, Br)] gave the corresponding alkali metal
terakis(carbochalcogenoato)-gallates and -indates M[M′
(EOCR)4] (M = Li, Na, K, Rb, Cs; M′ = Ga, In; E = S,
Se) in moderate to good yield, respectively. On the other
hand, the reactions with piperidinium carbodithioates under
similar conditions led to tris(carbodithioato)aluminum,
-gallium, and indium M(SSCR)3 (M = Al, Ga, In) in good
yields, respectively. X-Ray molecular structure analysis of
the carbothioate and selenoate derivatives revealed that the
tetrakis(carbochalcogenato) derivatives have a crystal sol-
vent such as an acetone molecule. These complexes were
found to react with methanol and iodomethane to give the
SCHEME 7 Reactions of the 4-methyl derivatives 10d and 11d
with various reagents
TABLE 7 The reaction conditions of compounds 10d and 11d with methanol, amines, iodomethane, and iodine and the yields of products
22-25
Reaction
M(SSCR)3
R
condition
Compd.
no.
Reactants
Temp. Time
M
A
10 or 11/A Solvent (°C)
MeOH 64
(h)
Products
Yielda (%)
4-CH3C6H4 Ga 10d
In 11d
Ga 10d
In 11d
Ga 10d
In 11d
Ga 10d
MeOH (excess)
CH2=CHCH2NH2
Et2NH
24
RCSOMe 22
76
26
1/4
1/4
1/4
CH2Cl2 25
CH2Cl2 25
CH2Cl2 25
2
2
2
RCSNHCH2CH= CH2 23a 81
85
RCSNEt2 23b
76
81
79
In
Ga 10d
In 11d
Ga 10d
In 11d
11d
74
-
-
90
86
MeI (excess)
I2 (excess)
MeI
42
24
1
no reaction
no reaction
(RCSSe)2 25
CH2Cl2 25
aIsolated yields.

NAKATA eT Al.
9 of 10
|
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SCHEME 8 Reactions of the 4-methyl derivatives 3c-6c or 10,
11 with I2
corresponding methyl ester and S- and Se-methyl thio- and
selenoesters in good yields. The reactions with primary and
secondary amines led to the corresponding amides in quantita-
tive yields.
The reactions of terakis-derivatives with iodine gave the
corresponding diacyl disulfides and diselenide in good yields.
These reagents attack to the carbon and dithiocarboxyl groups.
These findings may help us to understand not only organic
synthesis using carbochalcogenoate compounds but also the
biological activities of various organosulfur and -selenium
compounds.
[5] R. Köster, R. Kucznierz, G. Seidel, P. Betz, Chem. Ber. 1992, 125,
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W. Nakanishi, O. Niyomura, F. Ando, J. Koketsu, Dalton Trans.
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[9] a) N. Nakata, Bachelor Thesis of Gifu University (1998); b) N.
Nakata, Master These of Gifu University, 2000; A part of this
work was preliminarily presented; c) N. Nakata, O. Niyomura,
S. Kato, 76th Annual Meeting of the Chemical Society of Japan,
Yokohama, March 1999, (4C416); d) N. Nakata, O. Niyomura,
S. Kato, 78th Annual Meeting of the Chemical Society of Japan,
Chiba, March 2000, (4G310).
ACKNOWLEDGMENTS
[10] P. Singh, S. Bhattacharya, V. D. Gupta, H. Nöth, Chem. Ber. 1996,
129, 1093.
This research was supported by a Grant-in-Aid for Scientific
Research on Priority Areas and by Grants-in-Aid for
Scientific Research from the Ministry of Education, Science,
Sports and Culture of Japan. We thank Emeritus Professor
Takashi Kawamura and Professor Toshiaki Murai of Gifu
University for their helpful advice.
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ORCID
Norio Nakata
Shinzi Kato
https://orcid.org/0000-0003-4120-7924
https://orcid.org/0000-0002-3487-7228
Osamu Niyomura
https://orcid.org/0000-0003-1889-1334
https://orcid.org/0000-0001-7183-326X
[13] E. Jaskowska, L. Dobrzycki, P. Rzepinski, W. Ziemkowska, J.
Sulf. Chem. 2015, 36, 326.
Masahiro Ebihara
[14] a) H. Kageyama, K. Takagi, T. Murai, S. Kato, Z. Naturforsch.
1989, 44b, 1519; b) Y. Kawahara, S. Kato, T. Kanda, T. Murai, Z.
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Terashima, M. Mizuta, T. Katada, Z. Naturforsch. 1980, 35b, 458;
e) S. Kato, T. Murai, M. Ishida, Org. Prep. Proced. Int. 1986, 18,
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How to cite this article: Nakata N, Kato S, Niyomura
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