CM5071

NANYANG TECHNOLOGICAL UNIVERSITY

DIVISION OF CHEMISTRY AND BIOLOGICAL CHEMISTRY

SCHOOL OF PHYSICAL & MATHEMATICAL SCIENCES

Title: Reactivity of Nucleophilic

closo-hexaborate Cluster Dianion

Submitted by: SEAH XIAO JUN

(U2140850F)

Supervisor: Prof Rei Kinjo

Academic Year 2022/2023 Special Term I

Abstract
Group 13 species are generally known as Lewis acid and act as
electrophiles in chemical reactions. In the past 20 years, the study of the
nucleophilicity of boron has developed rapidly and comprehensively.
However, the nucleophilic behavior of closo-hexaborate cluster dianion
is relatively underdeveloped. Herein, the smallest known boron-based
cluster [B6H6]2- 2M+ has been synthesized to examine its reactivity with
the phosphine ligand and the B-H bond functionalization through the
bidentate phosphine ligand.

i
Table of Contents
Abstract…………………………………………………….………………………..i
Table of Contents………………………...….…….
………………………………..ii
1. Introduction……………………………………………….
……………………...1
1.1 Background……………………………………………………….………….1
1.2 Schemes and
Reactions…………………………………………....................3
2. Experimental Procedures………………………………………………………...7
2.1 Synthesis of 1,2-bis(tert-butylchlorophosphino)benzene……….……….
…...7
2.1.1 Synthesis of bis(diethylamino)chlorophosphine (Compound 1).
……....7
2.1.2 Synthesis of N,N,N’,N’–tetraethyl (2-bromophenyl) phosphonous acid
diamide (Compound 2)………………….…………………………………...8
2.1.3 Synthesis of 1,2-phenylenebis(N,N,N’,N’-tetraethylphosphinediamine)
(Compound 3) .
……………………………………………………………....9
2.1.4 Synthesis of 1,2-bis(dichlorophosphino)benzene (Compound 4)..
…...10
2.1.5 Synthesis of 1,2-bis(tert-butylchlorophosphino)benzene (Compound 5)
……………………………………………………………………………10
2.2 Synthesis of closo-hexaborate dianion [B6H6]2- 2M+
…………………..........11
2.2.1 Synthesis of [B6H6Hfac][NBu4] (Compound 6)..………………………
11
2.2.2 Synthesis of [B6H6][NBu4]2 (Compound 7)….…………………….…12

ii
 2.2.3 Synthesis of [B6H6Hfac][MePPh3] (Compound 8)…..…………………
13
2.3.4 Synthesis of [B6H6][MePPh3]2 (Compound 9)….…………………….13
3. Results and Analysis………………………………………………………........14
3.1 Bis(diethylamino)chlorophosphine (Compound 1)………..
………………..14
3.2 N,N,N’,N’–tetraethyl(2-bromophenyl) phosphonous acid diamide
(Compound
2)………………………………………………………………………….…….18
3.3 1,2-phenylenebis(N,N,N’,N’-tetraethylphosphinediamine) (Compound 3)
………………………………………………………………………………..22
3.4 1,2-bis(dichlorophosphino)benzene (Compound 4)..
……………………….26
3.5 1,2-bis(tert-butylchlorophosphino)benzene (Compound 5)..
….....................30
3.6 [B6H6Hfac][NBu4] (Compound 6)….…………………………..……………34
3.7 [B6H6][NBu4]2 (Compound 7)…………….………………………………...38
3.8 [B6H6Hfac][MePPh3] (Compound 8)……………..……….………..………..42
3.9 [B6H6][MePPh3]2 (Compound 9)………………………….…………..….…
47
4. Conclusion…………………………………………………………...................52
5. References………………………………………………………………………
52
6. Appendix………………………………………………………………………..

iii
1. Introduction
1.1 Background
Boron-based compounds have been widely used in synthetic organic
chemistry, material chemistry, and medicinal chemistry. 1 Boron is
traditionally characterized as Lewis acidic and electrophilic, while its
reactivity is predominantly described in terms of its Lewis acidity and its
behavior as an electrophile. Recent studies have highlighted its
nucleophilic behaviors and there is increasing focus on its reactions with
various electrophiles. In 2006, Yamashita, Nozaki, and Segawa
reportedly discovered the first nucleophilic boryllithium which is
isolable and can react with various carbon electrophiles.2

Figure 1. Examples of nucleophilic boron compounds.1

0
 In general, bulky ligands are essential in the synthesis of nucleophilic
boron compounds to reduce the high reactivity of the boron center.
However, this kind of steric protection has limited its application in
organic synthesis chemistry due to its instability when exposed to air.
Therefore, an alternative to stabilize the highly reactive nucleophilic
boron center is through the synthesis of closo-hexaborate cluster dianion
([B6H6]2- 2M+).3
Polyhedral boron clusters ([BnHn]2-, n = 6 - 12) have been introduced
by Lipscomb and co-workers in 1954 and show high stability due to the
three-dimensional electron delocalization.4 However, unlike [B12H12]2-
and [B10H10]2- which had been developed in extensive studies, [B 6H6]2-
was only synthesized and isolated ten years later due to the formation of
diborane in the process of synthesis, low yield and its decomposition in
acidic medium. In 1999, Preetz and co-workers have revealed that this
smaller boron cluster, however, exhibits significant nucleophilic
characteristics as compared to [B12H12]2-. This is because the maxima of
electron density are concentrated at the eight faces of the octahedron
structure. As a result, they are more prone to the attack of electrophiles
or the addition of facial proton (Hfac) to give [B6H6Hfac]-. This facial
proton potentially reduces the nucleophilicity of boron and can only be
eliminated using base.5
[B6H6]2- is a Brønsted base with a pKa value of 7, hence its protonated
form [B6H6Hfac]- is a weak acid. For a substitution step to occur, a neutral
or base solution is required and a strong base solution is necessary for
subsequent substitutions. Previous research has studied the substitution
reaction of [B6H6]2- and alkyl halides and revealed that an electrophilic
attack of the halogen atom to the region of octahedron facets had
occurred. 5
In light of the strong nucleophilicity and stability in the atmosphere,
we will be investigating the reactions of [B6H6]2- with a variety of
electrophilic substrates, mainly focusing on the formation of B-P bond.

1
1.2 Schemes and Reactions
In this project, 1,2-bis(tert-butylchlorophosphino)benzene
(Compound 5), closo-hexaborate dianion (Compound 7 and 9), and the
target compound (Compound 12) were synthesized as follows:

Scheme 1. Synthesis of 1.

Scheme 2. Synthesis of 2.

Scheme 3. Synthesis of 3.

2
Scheme 4. Synthesis of 4.

Scheme 5. Synthesis of 5.

Scheme 6. Synthesis of 6.

3
Scheme 7. Synthesis of 7.

Scheme 8. Synthesis of 8.

Scheme 9. Synthesis of 9.

4
With these compounds in hand, the functionalization of 7/9 will be
examined with compound 5 in the next step to synthesize the target
compound 12.

Scheme 10. The proposal route of synthesis compound 12.

5
2. Experimental Procedures
General Information
The reactions were mainly conducted under argon using the Schlenk line
or glovebox. All glassware was dried in an oven at 190 °C overnight
before use. Solvents were dried over Na metal or CaH 2 and collected
through a reflux system. PCl3 was distilled before use and other reagents
were used as received without further purification. The nuclear magnetic
resonance spectroscopy was recorded on a Bruker BBFO1 or BBFO2-
400 (1H 400.1 MHz; 31P 162.0 MHz; 11B 128.0 MHz) spectrometers at
298 K. 1H chemical shifts are referred to tetramethylsilane, 31P NMR
chemical shifts are relative to 85% H 3PO4, and 11B NMR chemical shifts
are relative to BF3·Et2O. The chemical shifts were denoted as δ in parts
per million (ppm). The following abbreviations were used in the report:
s = singlet, d = doublet, t = triplet, sect = sextet, m = multiplet, td =
triplet of doublets, br = broad signal, br s = broad singlet. The coupling
constant J was recorded in Hz.

2.1 Synthesis of 1,2-bis(tert-butylchlorophosphino)benzene

2.1.1 Synthesis of bis(diethylamino)chlorophosphine (Compound 1)

This step was conducted under argon gas. In a 500-mL round-bottom

flask, phosphorus trichloride (5.20 mL, 60.0 mmol) and 200 mL of dry
diethyl ether were added. The mixture was stirred and cooled to ‒20 °C
in an acetone/liquid nitrogen bath. At this temperature, diethylamine
(24.8 mL, 240 mmol) was added dropwise into the flask using a
pressure-equalizing funnel. The mixture was then warmed to room

6
temperature and stirred overnight. The precipitate was separated through
filtration, and the filtrate was concentrated under reduced pressure using
liquid nitrogen. Distillation was conducted under reduced pressure,
yielding 1 (6.65 g, 53% yield) as a colorless oil. 6 1H NMR (CDCl3, 400
MHz): δ 3.16 (br s, 8 H, CH2), 1.14 (t, J = 8.0 Hz, 12 H, CH3); 31P{1H}
NMR (CDCl3, 400 MHz): δ 160.1 (s).

2.1.2 Synthesis of N,N,N’,N’–tetraethyl (2-bromophenyl)

phosphonous acid diamide (Compound 2)

In a 200-mL round-bottom flask, 1,2-dibromobenzene (6.45 g, 27.4

mmol) was added into a mixture of dry diethyl ether (50.0 mL) and
tetrahydrofuran (50.0 mL). The mixture was stirred and cooled to ‒130
°C in an ethanol/liquid nitrogen bath. At this temperature, n-butyllithium
(2.0 M in hexane, 14.0 mL, 28.0 mmol) was added dropwise into the
flask using a syringe and stirred for 30 minutes. 1 (6.00 g, 28.5 mmol) in
a mixture of dry diethyl ether (50.0 mL) and tetrahydrofuran (50.0 mL)
was added dropwise into the flask using a pressure-equalizing funnel
and stirred for 60 minutes. The resulting mixture was then warmed to
room temperature and stirred overnight. 100 mL of ice water was added
to the resulting solution and then extracted with 200 mL of n-pentane.
The organic layer was separated, dried over anhydrous magnesium
sulphate and filtered. Solvents were removed in the rotary evaporator.
The residue was concentrated under reduced pressure using liquid
nitrogen at 55 °C, resulting in a yellow viscous oil (7.65 g, 84% yield).
The crude product was used without further purification. 7 1H NMR
7
(C6D6, 400 MHz): δ 7.49 (m, 1 H, CH), 7.43 (m, 1 H, CH), 7.06 (m, 1 H,
CH), 6.75 (m, 1 H, CH), 3.02 (m, 8 H, CH2), 1.02 (t, J = 6.0 Hz, 12 H,
CH3); 31P{1H} NMR (C6D6, 400 MHz): δ 96.4 (s).

2.1.3 Synthesis of 1,2-phenylenebis(N,N,N’,N’-

tetraethylphosphinediamine) (Compound 3)

2 (7.65 g, 23.1 mmol) was added to 60.0 mL of dry tetrahydrofuran and

cooled to ‒78 °C in an acetone/liquid nitrogen bath. At this temperature,
n-butyllithium (2.0 M in hexane, 12.0 mL, 24.0 mmol) was added
dropwise into the flask using a syringe and stirred for further 30 minutes.
1 (4.70 g, 22.3 mmol) dissolved in 15.0 mL of tetrahydrofuran was
added dropwise into the flask using a pressure-equalizing funnel and
stirred for 30 minutes. The resulting mixture was warmed to room
temperature and stirred overnight. Solvent was removed in vacuo where
the residue was filtered with 60.0 mL of n-pentane. The filtrate was
concentrated under reduced pressure using liquid nitrogen at 45 °C to
give 3 (9.46 g, 96% yield) as a yellowish oil. The crude product was
used without further purification. 7 1H NMR (C6D6, 400 MHz): δ 7.77
(m, 2 H, CH), 7.27 (m, 2 H, CH), 3.12 (m, 16 H, CH2), 1.10 (t, J = 4.0
Hz, 24 H, CH3); 31P{1H} NMR (C6D6, 400 MHz): δ 98.1 (s).

8
2.1.4 Synthesis of 1,2-bis(dichlorophosphino)benzene (Compound 4)

3 (9.46 g, 22.2 mmol) was added to 50.0 mL of dry tetrahydrofuran and

cooled to ‒78 °C in an acetone/liquid nitrogen bath. At this temperature,
HCl in diethyl ether (2.0 M in hexane, 230 mL, 460 mmol) was added
dropwise using a pressure-equalizing funnel and stirred for further 15
minutes. The resulting mixture was then warmed to room temperature
and stirred overnight. Solvent was removed in vacuo at 45 °C for two
hours. The residue was dissolved in 50.0 mL of n-pentane and filtered
(ca. two times). Subsequently, the filtrate was concentrated under
reduced pressure using liquid nitrogen again, yielding 4 (2.70 g, 44%
yield) as a clear colorless oil. 7 1H NMR (400 MHz, C6D6): δ 7.79 (m, 2
H, CH), 6.88 (m, 2 H, CH); 31P{1H} NMR (400 MHz, C6D6): δ 151.6 (s).

2.1.5 Synthesis of 1,2-bis(tert-butylchlorophosphino)benzene

(Compound 5)

This step was conducted under argon gas. To a 500-mL two-necked

round-bottom flask, magnesium (1.11 g, 45.7 mmol) and 20.0 mL of dry
9
diethyl ether were added. tBuCl (4.90 mL, 46.1 mmol) dissolved in 14
mL of diethyl ether was added dropwise into the flask using a pressure-
equalizing funnel at room temperature and stirred vigorously. 8 4 (2.60 g,
9.29 mmol) dissolved in 70.0 mL of tetrahydrofuran was cooled to ‒78
°C in an acetone/liquid nitrogen bath. At this temperature, the resulting
tBuMgCl solution was added into the flask containing 4. The mixture
was then warmed to room temperature and stirred overnight. Solvent
was removed in vacuo, and the residue was filtered with
dichloromethane. The filtrate was concentrated under reduced pressure
using liquid nitrogen, yielding 5 (2.84 g, 54% yield) as a pale-yellow oil.
9 1
H NMR (CD3CN, 400 MHz): δ 7.90 (m, 2 H, CH), 7.58 (m, 2 H, CH),
1.11 (t, J = 8.0 Hz, 18 H, CH3); 31P{1H} NMR (CD3CN, 400 MHz): δ
107.5 (s).

2.2 Synthesis of closo-hexaborate dianion [B6H6]2- 2M+

2.2.1 Synthesis of [B6H6Hfac][NBu4] (Compound 6)

Na2B6H6 was dissolved in water, and tetrabutylammonium bromide

(15.0 g, 46.5 mmol) dissolved in 200 mL of water was added to the
solution. The large amount of white precipitate was filtered out, washed
with water and air-dried for hours. Subsequently, the solid was dissolved
in hot methanol (170 mL) and ethanol (170 mL), filtered and cool to
room temperature before being kept in the refrigerator overnight,

10
yielding a white crystalline solid (4.27 g, 35%).10 1H NMR (CDCl3, 400
MHz): δ 3.19 (m, 8 H, CH2), 1.59 (m, 8 H, CH2), 1.45 (sext, J = 7.2 Hz,
8 H, CH2), 1.00 (t, J = 6.0 Hz, 12 H, CH3), -5.29 (s, 1 H, facial proton);
11
B NMR (CDCl3, 400 MHz): δ -13.5 (d, J = 448.0 Hz, 6 B); 11B{1H}
NMR (CDCl3, 400 MHz): δ -13.5 (s).

2.2.2 Synthesis of [B6H6][NBu4]2 (Compound 7)

This step was carried out under inert condition. After adding 6 and dry
dichloromethane to a 100-mL round-bottom flask, tetrabutylammonium
hydroxide (TBAOH) was added dropwise via a syringe to the flask. The
mixture was stirred for three hours after adding sodium sulphate in two
portions into the flask. The solid was filtered and the filtrate was
concentrated under reduced pressure using liquid nitrogen, forming 7
(1.64 g, 92%).3 1H NMR (CDCl3, 400 MHz): δ 3.31 (m, 8 H, CH2), 1.63
(m, 8 H, CH2), 1.44 (sext, J = 8.0 Hz, 8 H, CH2), 0.97 (t, J = 8.0 Hz, 12
H, CH3); 11B NMR (CDCl3, 400 MHz): δ -13.6 (d, J = 440.0 Hz, 6 B);
11
B{1H} NMR (CDCl3, 400 MHz): δ -13.5 (s).

11
2.2.3 Synthesis of [B6H6Hfac][MePPh3] (Compound 8)

Na2B6H6 (4.55 g, 38.9 mmol) was dissolved in water, and

methyltriphenylphosphonium bromide (15.3 g, 42.8 mmol) was added to
the flask and stirred. The mixture was filtered, where the solid was
washed with water and dried under vacuum. Hot methanol and ethanol
were used in recrystallization to give white crystalline solid (5.14 g,
38%).3 1H NMR (CD2Cl2, 400 MHz): δ 7.88 (m, 3 H, CH), 7.73 (td, J =
7.2, 3.6 Hz, 6 H, CH), 7.65 (m, 6 H, CH), 2.84 (d, J = 12.0 Hz, 3 H,
CH3), -5.48 (br s, 1 H, facial proton); 11B NMR (CD2Cl2, 400 MHz): δ -
14.6 (d, J = 452.0 Hz, 6 B); 11B{1H} NMR (CD2Cl2, 400 MHz): δ -14.6
(s); 31P{1H} NMR (CD2Cl2, 400 MHz): δ 20.9 (s).

2.2.4 Synthesis of [B6H6][MePPh3]2 (Compound 9)

12
In a 200 mL round-bottomed flask that contained
methyltriphenylphosphonium bromide (7.12 g, 19.9 mmol) and 40.0 mL
of dry diethyl ether, n-butyllithium (2.0 M in hexane, 10.5 mL, 20.9
mmol) was added dropwise into the flask using a syringe and stirred
overnight. The orange solution was filtered and concentrated under
reduced pressure to give methylenetriphenylphosphorane (3.14 g, 57%).
It was then dissolved in 10.0 mL of dry tetrahydrofuran and added to the
flask containing 8 and 15.0 mL of dry tetrahydrofuran. The mixture was
stirred overnight, the solid was collected through filtration and dried
under vacuum to give 9 (1.34 g, 77%) as the final product. 3 1H NMR
(CDCl3, 400 MHz): δ 7.77 (m, 9 H, CH), 7.62 (m, 6 H, CH2), 3.43 (d, J
= 13.0 Hz, 3 H, CH3); 11B NMR (CDCl3, 400 MHz): δ -12.8 (d, J =
119.3 Hz, 6 B); 11B{1H} NMR (CDCl3, 400 MHz): δ -12.8 (s); 31P{1H}
NMR (CDCl3, 400 MHz): δ 21.7 (s).

3. Results and Analysis

a) Bis(diethylamino)chlorophosphine (Compound 1)

When phosphorus trichloride reacted with diethylamine at ‒20 °C and

warmed to room temperature overnight, a light-yellow solution with pale
yellow precipitate was obtained. After the product was filtered,
concentrated, and distilled under reduced pressure, a colorless oil with a
53% yield was obtained. The low yield arose from the loss of product
that occurred during the distillation as there may be heat lost to the
surroundings and the product was not distilled out. Hence, when
performing this step for the second time, an aluminium foil was used to
cover the apparatus to prevent heat loss and ensure that 1 can reach its
boiling point under limiting reduced pressure.

13
The product was considered pure based on the 1H NMR and 31
P{1H}
NMR spectra shown in Figure 2 and Figure 3.

CDCl3

Figure 2. 1H NMR spectrum of 1 in CDCl3.

14
Figure 3. 31P{1H} NMR spectrum of 1 in CDCl3.

15
 HB

CDCl3
HA

Figure 4. Assignment of proton in 1H NMR spectrum of 1.

HA has a larger chemical shift and appears in the downfield peak because
it is closer to the nitrogen atom which is very electronegative that can
pull electrons away from HA, causing it to be more deshielded. The
peaks appearing at around 1.21 ppm and 3.48 ppm come from diethyl
ether, which is the solvent used and becomes the impurity in the product.

16
Figure 5. Reaction mechanism to form 1.
PCl3 acts as an electrophile due to the presence of empty d orbitals that
can accept electrons from nitrogen. The surrounding chlorine atoms also
pull the electron away from the phosphorus center, making it electron
deficient. The equivalence of diethylamine to PCl 3 is 4:1, indicating that
two molecules of diethylamine are needed to react with PCl 3 to form 1,
while another 2 molecules of diethylamine reacted with Cl - to form
precipitates.

b) N, N, N’, N’ – tetraethyl (2-bromophenyl) phosphonous acid

diamide (Compound 2)

The reaction between 1, 1,2-dibromobenzene, and n-butyllithium gave a

yellow solution. The subsequent workup was conducted under non-inert
conditions which yielded a yellow viscous oil with 84% yield. The
product was relatively pure as reflected in the 1H NMR and 31P{1H}
NMR spectra shown in Figure 6 and Figure 7.

17
 C6D6

Figure 6. 1H NMR spectrum of 2 in C6D6.

18
Figure 7. 31P{1H} NMR spectrum of 2 in C6D6.

19
 HF

HE

: HA
: HB
: HC
: HD
: C6D6

Figure 8. Assignment of proton in 1H NMR spectrum of 2.

The aromatic protons appear in the downfield peak because the applied
magnetic field induced an opposing magnetic field in the π-system.
While bromine is more electronegative than phosphorus, the protons
close to bromine are more deshielded than those close to phosphorus. H E
becomes a multiplet because it is spin-coupled to H F and also HE on the
other ethyl attached to the same nitrogen.

20
Figure 9. Reaction mechanism to form 2.
N-butyllithium is a strong nucleophile that can attack 1,2-
dibromobenzene to generate carbanion. This carbanion act as a
nucleophile to attack ClP(NEt2)2 to form the final product.
1-bromobutane is soluble in diethyl ether, thus it was removed together
with the solvent in the rotary evaporator. Lithium chloride which is
water-soluble was removed from the product during extraction where the
aqueous layer was discarded.

c) 1,2-phenylenebis(N, N, N’, N’ - tetraethylphosphinediamine)

(Compound 3)

The crude product reacted with 1 and n-butyllithium, resulting in a

reddish-brown solution. The product was concentrated, filtered and
concentrated again to give a yellowish viscous oil with 96% of yield. A
relatively pure product was expected from the 1H NMR and 31P{1H}
NMR spectra shown in Figure 10 and Figure 11.

21
 C6D6

Figure 10. 1H NMR spectrum of 3 in C6D6.

22
Figure 11. 31P{1H} NMR spectrum of 3 in C6D6.

23
 HD

HC
HA HB C6D6

Figure 12. Assignment of proton in 1H NMR spectrum of 3.

The aromatic protons were expected to appear in the downfield. As H A is
closer to the electronegative phosphorus, it is more electron deficient
and hence more deshielded than HB. HC is a multiplet due to the spin-
spin coupling with HD and HC.

24
Figure 13. Reaction mechanism to form 3.
Similarly, N-butyllithium carry out nucleophilic attack on to form a
carbanion which can then act as a nucleophile to attack ClP(NEt 2)2 to
form the final product.
The by-products were removed in similar manners where 1-
bromobutane was removed along with the solvent and lithium chloride
was removed during filtration with n-pentane.

d) 1,2-bis(dichlorophosphino)benzene (Compound 4)

The product from 3 and HCl in diethyl ether was a colorless solution
with a large amount of white precipitate. The product was concentrated,
filtered and concentrated again to give a clear colorless with a relatively
low yield (44%). The low yield may be due to the loss of product during
removal of solvent as some product could be dissolved in the solvent.
There are impurities and by-products presented in the product based on
the 1H NMR spectrum shown in Figure 14.

25
 C6D6

Figure 14. 1H NMR spectrum of 4 in C6D6.

26
Figure 15. 31P{1H} NMR spectrum of 4 in C6D6.

27
 Silicon grease

C6D6
HA HB

Figure 16. Assignment of proton in 1H NMR spectrum of 4.

The peak at approximately δ 2.93 and δ 0.89 may belong to the by-
product (diethylamine hydrochloride). The peak at δ 0.28 belongs to the
silicone grease that was used on the glassware.

Figure 17. Reaction between 5 and HCl to form 6.

Diethylamine hydrochloride is soluble in water, therefore the extraction
using n-pentane was repeated for two times to remove most of the by-
product. However, from the 1H NMR spectrum, diethylamine

28
hydrochloride still existed in the product, Hence, the extraction should
be repeated for a few more times to ensure complete removal of
diethylamine hydrochloride.

e) 1,2-bis(tert-butylchlorophosphino)benzene (Compound 5)

The product yielded from 4 and tBuMgCl was a pale yellow solution.
After the removal of solvent, filtration and concentrated under reduced
pressure, the product became a pale yellow oil which solidified later.
The yield is moderately low (54%) because during the preparation of
tBuMgCl, the magnesium did not fully reacted with tBuCl, some of the
magnesium was suspended in the solution. It may be necessary to heat at
reflux to drive the reaction to completion.
From the 1H NMR spectrum, the product was considered relatively pure,
with some solvent peaks presented.

29
 CD3CN

Figure 18. 1H NMR spectrum of 5 in CD3CN.

30
Figure 19. 31P{1H} NMR spectrum of 5 in CD3CN.

31
 HC

THF
CD3CN THF
H HB
A

Figure 20. Assignment of proton in 1H NMR spectrum of 5.

Tetrahydrofuran was the solvent used in this step and it was not
completely removed from the product. Its signals appeared at δ 3.68 and
δ 1.81. Meanwhile, acetonitrile appeared at δ 1.94.

32
Figure 21. Reaction mechanism to form 5.
Grignard reagent is a good nucleophile that can react with 1,2-
bis(dichlorophosphino) benzene to form the final product.
Magnesium chloride is highly soluble in water and can be removed by
extraction with dichloromethane.

f) [B6H6Hfac][NBu4] (Compound 6)

White crystalline solid was formed after recrystallization from methanol

and ethanol. When filtering the crystals from the residual solvent, the
flask was washed with methanol (at room temperature instead of cold

33
methanol), causing some of the crystals to dissolve in methanol and led
to a low yield (35%) with relatively high purity.

CDCl3

Figure 22. 1H NMR spectrum of 6 in CDCl3.

34
Figure 23. 11B NMR spectrum of 6 in CDCl3.

35
Figure 24. 11B{1H} NMR spectrum of 6 in CDCl3

36
 CH3

CH2
CH2
CDCl3 CH2
Hfac

Figure 25. Assignment of proton in 1H NMR spectrum of 6.

On [NBu4]+, the closer the protons to the electronegative nitrogen atom,
the more deshielded they are.

g) [B6H6][NBu4]2 (Compound 7)

The product was a white solid with 92% of yield and showed high purity
according to the NMR spectra.

37
 CDCl3

Figure 26. 1H NMR spectrum of 7 in CDCl3.

38
Figure 27. 11B NMR spectrum of 7 in CDCl3.

39
Figure 28. 11B{1H} NMR spectrum of 7 in CDCl3

40
 CH3

CDCl3

CH2
CH2 CH2

Figure 29. Assignment of proton in 1H NMR spectrum of 7.

The positions of signals are similar to those of 6 with the absence of Hfac
peak indicates that the reaction has completed.

3.8 [B6H6Hfac][MePPh3] (Compound 8)

The product was a white crystalline solid with a low yield (38%). It was
because the after adding triphenylphosphonium bromide into Na2B6H6,

41
the mixture was not stirred for three hours and led to incomplete
reaction, resulting in loss of product. However, the product was
considered pure based on the NMR spectra shown below.

CD2Cl2

Figure 30. 1H NMR spectrum of 8 in CD2Cl2.

42
Figure 31. 11B NMR spectrum of 8 in CD2Cl2.

43
Figure 32. 11B{1H} NMR spectrum of 8 in CD2Cl2.

44
Figure 33. 31P{1H} NMR spectrum of 8 in CD2Cl2.

45
 CH3

CH

CD2Cl2

B-H Hfac

Figure 34. Assignment of proton in 1H NMR spectrum of 8.

The aromatic protons appear in downfield (δ 7.88, 7.73, 7.65) while the
methyl protons are more shielded and hence appear in upfield (δ 2.84).

3.9 [B6H6][MePPh3]2 (Compound 9)

46
After the solid was collected through filtration and dried in vacuo, a
yellow powder was obtained with 77% of yield. The NMR spectra
indicates that the product was moderately pure.

CDCl3

Figure 35. 1H NMR spectrum of 9 in CDCl3.

47
Figure 36. 11B NMR spectrum of 9 in CDCl3.

48
Figure 37. 11B{1H} NMR spectrum of 9 in CDCl3.

49
Figure 38. 31P{1H} NMR spectrum of 9 in CDCl3

50
 CDCl3

CH
CH3

Figure 39. Assignment of proton in 1H NMR spectrum of 9.

The positions of signals are similar to those of 8 with the absence of Hfac
peak indicates that the reaction has completed.

4. Conclusion
In this project, a variety of compounds have been prepared for the
synthesis of the final compound. The reactivity of closo-hexaborate
cluster will be investigated through the reaction with the phosphine
ligand.

5. References

51
1. Pécharman, A.-F., Colebatch, A. L., Hill, M. S., McMullin, C. L.,
Mahon, M. F., & Weetman, C. (2017). Easy access to nucleophilic
boron through diborane to magnesium boryl metathesis. Nature
Communications, 8(1).
2. Segawa, Y., Yamashita, M., & Nozaki, K. (2006). Boryllithium:
Isolation, characterization, and reactivity as a boryl anion. Science,
314(5796), 113–115.
3. Mu, X., Axtell, J. C., Bernier, N. A., Kirlikovali, K. O., Jung, D.,
Umanzor, A., Qian, K., Chen, X., Bay, K. L., Kirollos, M.,
Rheingold, A. L., Houk, K. N., & Spokoyny, A. M. (2019). Sterically
unprotected nucleophilic boron cluster reagents. Chem, 5(9), 2461–
2469.
4. Eberhardt, W. H., Crawford, B., & Lipscomb, W. N. (1954). The
valence structure of the boron hydrides. The Journal of Chemical
Physics, 22(6), 989–1001.
5. Preetz, W., & Peters, G. (1999). The hexahydro-closo-hexaborate dianion
[B6H6]2– and its derivatives. European Journal of Inorganic Chemistry,
1999(11), 1831–1846.
6. Qin, L., Ren, X., Lu, Y., Li, Y., & Zhou, J. S. (2012). Intermolecular
Mizoroki-Heck reaction of aliphatic olefins with high selectivity for
substitution at the internal position. Angewandte Chemie, 124(24),
6017–6021.
7. Bresien, J., Michalik, D., Schulz, A., Villinger, A., & Zander, E.
(2020). Azadiphosphaindane‐1,3‐diyls: A class of resonance‐
stabilized biradicals. Angewandte Chemie, 60(3), 1507–1512.
8. Köster, M., Kreher, A., & von Hänisch, C. (2018). Synthesis of
ternary group 13/15 chain compounds. Dalton Transactions, 47(24),
7875–7878.
9. Kyba, E. P., Kerby, M. C., & Rines, S. P. (1986). A convenient
synthesis of symmetrical and unsymmetrical 1,2-
bis(phosphino)benzenes as ligands for transition metals.
Organometallics, 5(6), 1189–1194.

52
10. Kabbani, R. M. (1996). High yield synthesis of [(C 4H9)4N][Ni(η5-
C5H5)B6H6]. Polyhedron, 15(12), 1951–1955.

6. Appendix
NMR Spectra

Figure 6a. 1H NMR spectrum of 1 in CDCl3.

53
Figure 6b. 31P{1H} NMR spectrum of 1 in CDCl3.

54
Figure 6c. 1H NMR spectrum of 2 in C6D6.

55
Figure 6d. 31P{1H} NMR spectrum of 2 in C6D6.

56
Figure 6e. 1H NMR spectrum of 3 in C6D6.

57
Figure 6f. 31P{1H} NMR spectrum of 3 in C6D6.

58
Figure 6g. 1H NMR spectrum of 4 in C6D6.

59
Figure 6h. 31P{1H} NMR spectrum of 4 in C6D6.

60
Figure 6i. 1H NMR spectrum of 5 in CD3CN.

61
Figure 6j. 31P{1H} NMR spectrum of 5 in CD3CN.

62
Figure 6k. 1H NMR spectrum of 6 in CDCl3.

63
Figure 6l. 11B NMR spectrum of 6 in CDCl3.

64
Figure 6m. 11B{1H} NMR spectrum of 6 in CDCl3

65
Figure 6n. 1H NMR spectrum of 7 in CDCl3.

66
Figure 6o. 11B NMR spectrum of 7 in CDCl3.

67
Figure 6p. 11B{1H} NMR spectrum of 7 in CDCl3

68
Figure 6q. 1H NMR spectrum of 8 in CD2Cl2.

69
Figure 6r. 11B NMR spectrum of 8 in CD2Cl2.

70
Figure 6s. 11B{1H} NMR spectrum of 8 in CD2Cl2.

71
Figure 6t. 31P{1H} NMR spectrum of 8 in CD2Cl2.

72
Figure 6u. 1H NMR spectrum of 9 in CDCl3.

73
Figure 6v. 11B NMR spectrum of 9 in CDCl3.

74
Figure 6w. 11B{1H} NMR spectrum of 9 in CDCl3.

75
Figure 6x. 31P{1H} NMR spectrum of 9 in CDCl3

76