1,3,2-Dithiaphospholanes with an annelated 1,2-dicarba-closo- dodecaborane(12) unit: Formation and reactivity

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1,3,2-Dithiaphospholanes with an annelated

1,2-dicarba-closo-dodecaborane(12) unit:

formation and reactivity†

Cite this: Dalton Trans., 2014, 43,

5021

Bernd Wrackmeyer,*^aElena V. Klimkina^aand Wolfgang Milius^b

1,3,2-Dithiaphospholanes were prepared, containing an annelated 1,2-dicarba-closo-dodecaborane(12)

unit, bearing halogens (F, Cl, Br, and I), H, NEt₂, OEt groups, or organo substituents (R = i-Pr, t-Bu, Cy,

3,5-Me₂-C₆H₃-CH₂, Ph) at phosphorus. The t-Bu derivative was structurally characterised as its sulﬁde.

The organo-substituted derivatives escape the ring strain by irreversible (R = t-Bu; X-ray analysis) or

reversible dimerisation, by which 10-membered rings are formed. Using 1,1-bis(dichlorophosphino)-

methane, another dimer containing a 14-membered ring could be isolated and structurally characterised.

The preferred conformation of the 1,3,2-dithiaphospholanes depends on the nature of the substituent at

phosphorus. For instance, the substituents R = t-Bu, NEt₂prefer the equatorial position, as indicated by

diagnostic NMR data, supported by DFT calculations [B3LYP/6-311+G(d,p) level of theory]. The calcu-

lations also predict the tendency for dimerisation, and calculated NMR parameters are in good agreement,

in most cases, with experimental data.

Received 2nd October 2013,

Accepted 29th October 2013

DOI: 10.1039/c3dt52753k

www.rsc.org/dalton

rigid carborane skeleton is expected to contribute. Apparently,

its kinetically stabilizing eﬀect is more than compensated by

Introduction

Important compounds in the well developed chemistry of 1,2- its rigidity, enforcing contacts either with the respective substi-

dicarba-closo-dodecaborane(12) (“ortho carborane”)^1–3are tuent at phosphorus or the lone pair of electrons at phos-

derived from the dithiolate dianion [1,2-S₂-B₁₀H₁₀C₂]²⁻, which phorus.¹⁹If this is true, then 1,3,2-dithiaphospholanes should

is readily available by various methods as the dilithium- (1) or be more stable than their oxygen analogues because of the

the disodium salt.^4–7It serves as a versatile ligand in transition longer C–S and P–S bond lengths in comparison with the C–O

metal chemistry,^5,6,8–15and some main group element deriva- and P–O bond lengths in 2. Thus, we have set out to prepare

tives have been reported.^4,7,15–18Recently, we have prepared such 1,3,2-dithiaphospholanes with an annelated carbor-

1,3,2-dioxaphospholanes 2 starting from phosphorus halides ane^4,23to study their behaviour, using NMR spectroscopic

and the diolate dianion [1,2-O₂-B₁₀H₁₀C₂]²⁻(Scheme 1).¹⁹Such methods, quantum chemical calculations and X-ray crystallo-

phospholanes 2 with various substituents at phosphorus graphy. Moreover, these compounds could serve as attractive

turned out to be short-lived, and the 10-membered cyclic ligands in transition metal chemistry, considering the donor

dimers 3 were observed for the organo-substituted derivatives, capability of phosphorus and sulfur as well as the reactivity of

even with bulky substituents R. This was attributed to ring the P–S bonds.

strain and repulsive steric interactions in the 5-membered

rings.

Indeed, in contrast to numerous 1,3,2-dioxaphospholanes,

for which dimerisation appears to be fairly common,²⁰the

analogous 1,3,2-dithiaphospholanes tend to stay as mono-

mers.^21,22Considering repulsive interactions, the annelated

Results and discussion

Synthesis, characterisation of the compounds and first aspects

of reactivity

For the synthesis of the target compounds either the dilithium

salt 1 or the silane 4 (Scheme 2) can be considered as poten-

tially useful in reactions with phosphorus halides. Compound

4 has not been described so far. However, 4 is readily available

following the procedure reported for the corresponding

selenium derivative.²⁴Cleavage of the S–Si bonds in 4 in reac-

tions with phosphorus halides appeared to be promising.

^aAnorganische Chemie II, Universität Bayreuth, Universitätsstr. 30, D-95440

Bayreuth, Germany. E-mail: b.wrack@uni-bayreuth.de,

elena.klimkina@uni-bayreuth.de; Fax: +49-921-552157

^bAnorganische Chemie I, Universität Bayreuth, Universitätsstr. 30, D-95440

Bayreuth, Germany. E-mail: wolfgang.milius@uni-bayreuth.de

†CCDC 961682–961684. For crystallographic data in CIF or other electronic

format see DOI: 10.1039/c3dt52753k

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Scheme 1 Synthesis of 1,3,2-dioxaphospholanes 2 and their dimerisation to 3.

Scheme 2 Synthesis of starting materials 1 and 4.

Scheme 3 Reaction of the dilithium salt 1 with t-BuPCl₂in toluene or in Et₂O.

Studying the reaction of 1 with t-BuPCl₂under various con- readily with phosphorus trihalides PX₃(Scheme 4) to give the

ditions (Scheme 3) aﬀorded the desired compound 5 or its desired products 8a–c. These compounds are extremely reac-

dimer 6. When the reaction was carried out in toluene, 5 was tive, and tend to disproportionate towards a trithiophosphite

accompanied by its sulfide 7(S), indicating the diﬃculty of pre-

paring pure samples of 1. Adding THF to the solution contain-

9

²⁵and traces of products caused by hydrolysis such as 10.

The chloride 8a and the bromide 8b were used in several

ing 5 and 7(S), 5 was converted into its dimer 6 (characterised reactions in order to obtain at least NMR spectroscopic evi-

by X-ray structural analysis, vide infra) within a few minutes at dence for the parent phosphine 11 and the fluoride 12

r.t. Thus, dimerisation of the 5-membered ring also appears to (Scheme 5). Treatment of 8b with Bu₃Sn–H²⁶aﬀorded the

be a common feature for 1,3,2-dithiaphospholanes, similar to phosphine 11 in mixture with PH₃, 9, 10 and Bu₃Sn–Br, with a

1,3,2-dioxaphospholanes, depending on substituents. The role lifetime suﬃcient to measure the most relevant NMR data

of the solvent in the dimerisation process is noteworthy. (Fig. 2).

Neither 5 nor 7(S) were obtained from the reaction of 1 with

1

The particular conformation of 11 is supported by H, ³¹P

t-BuPCl₂in ether; instead the dimer 6 was the sole product. and ¹¹B NMR experiments (Fig. 2). Some features are note-

Interestingly, 7(S) was a side product when 5 was treated with worthy, e.g. the splitting of the ¹H(PH) NMR signal not only by

selenium to give the selenide 7(Se) (Fig. 1). Crystalline samples ³¹P–¹H spin–spin coupling but also by homonuclear coupling

of 7(S) could be obtained, suitable for X-ray structural analysis to ¹H(3) [Fig. 2(A,B)], which might be a through space coup-

(vide infra).

ling. Moreover, the ³¹P NMR signal also shows additional split-

1

Problems which may arise because of the elemental sulfur ting attributable to this H(3) [Fig. 2(C)]. We note the isotope-

present in 1 can be avoided using the silane 4. Thus, 4 reacts induced chemical shift ¹Δ^32/34S(³¹P) = −17 ppb.²⁷Although

5022 | Dalton Trans., 2014, 43, 5021–5043

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spectroscopic evidence for the formation of the phosphenium

cation [B₁₀H₁₀C₂S₂P]⁺.²⁹

The phosphorus halides 8 are potentially useful in silazane

cleavage reactions (Scheme 5). As an example, the benzylamino

derivative 15 was prepared in order to study its preferred con-

formation (indicated in Scheme 5) by NMR spectroscopy in

solution. The relatively large magnitude of the geminal coup-

ling constant ²J(³¹P,N,¹³C_(benzyl)) = +19.7 Hz, in agreement with

calculations, is taken as evidence for the preferred syn-posi-

tions of the assumed orientations of the lone pair of electrons

at phosphorus and the N–C bond vector (Table 2).^30,31

The reactions of the silane 4 with diethylamino- or ethoxy-

phosphorus dichloride (Scheme 6) proceed straightforwardly

to the corresponding 1,3,2-dithiaphospholanes 16 and 17,

which stay as monomers under all conditions studied (by con-

trast to the analogous 1,3,2-dioxaphospholanes¹⁹). On the

basis of NMR data (see Table 2 and Fig. 3), we propose

diﬀerent conformations for 16 and 17, as indicated in

Scheme 6.

Although the silane 4 reacts with organophosphorus di-

halides by S–Si bond cleavage, the reactions are somewhat

complex. The equimolar reaction gives in principle two pro-

ducts, monomers (5, 18–21) and dimers (6, 22–25) (Scheme 7,

Tables 2 and 3). The monomers are formed as the major

product. Complete S–Si bond cleavage was indicated after 1 h

at r.t. (R = i-Pr, Cy, 3,5-Me₂C₆H₃-CH₂, Ph); the progress of these

reactions can be monitored conveniently by ³¹P and ²⁹Si NMR

spectroscopy. The monomer/dimer ratio depends on the R

group at phosphorus, on the nature of the solvent used, the

reaction conditions as well as on the solubility of the com-

pounds and the equilibrium in the solution (see the Experi-

mental procedure). Because of the bulkyness of the t-Bu group,

the reaction of 4 with t-BuPCl₂becomes slow. The formation

of the monomer–dimer mixture (5/6) is accompanied by non-

cyclic derivatives in various amounts such as diastereomers

Fig. 1 NMR spectra of the reaction solution obtained from the reaction

of 5 with Se (in CD₂Cl₂, at 25 °C). (A) 202.5 MHz ³¹P{¹H} NMR spectrum

after 3 h at 50 °C in CD₂Cl₂, the mixture of 5, 7(S), 7(Se) and 6. The ⁷⁷Se

satellites are marked by arrows. (B) 95.4 MHz ⁷⁷Se{¹H} NMR spectrum of

the same mixture as in (A).

there is partial overlap of the ¹H(B) NMR signals [Fig. 2(F)], the

¹¹B NMR signals are well resolved [Fig. 2(G)], and the δ¹¹B

values are in reasonable agreement [Fig. 2(H)] with the calcu-

lated data.²⁸

The chloride 8a was partially converted into the fluoride 12.

The reaction mixture also contained the antimony fluoride 13

(Table 1) together with 9, 10, HPF₂, PF₃and unidentified

species. The presence of 12 is readily apparent by the ¹⁹F and

³¹P NMR spectra (Table 2). The exchange reaction of 8b with

BBr₃gave the boron bromide 14 (Scheme 5, Table 1). Attempts

to abstract chloride or bromide from 8a or 8b, respectively,

using AlCl₃, AlBr₃or silver triflate, failed. There was no NMR

Scheme 4 Cleavage of the S–Si bonds in the silane 4 by reaction with phosphorus trihalides PX₃.

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Scheme 5 Some reactions of the phosphorus halides 8a, b.

3

B₁₀H₁₀C₂[SP(t-Bu)Cl]₂26 and other unidentified intermediate doublets in ³¹P NMR spectra for 33 with J(³¹P,³¹P) = 20.1 Hz,

products. The existence of 26 was shown independently by the and a singlet, the typical region for 34).

reaction of 4 with two equivalents of t-BuPCl₂.

Calculated gas phase structures and NMR parameters

The dimers appear to be fairly unreactive except for hydro-

lysis. Thus, ³¹P NMR spectra indicate that the dimer 6 is not in

Except for the fairly large molecules 30, 33, 34, the gas

equilibrium with its monomer, even after prolonged periods of

time at 90 °C in [D₈]toluene. In contrast, monomers are rever-

sibly formed after heating samples of the dimers 22 or 25 dis-

solved in [D₈]toluene at 90 °C. The 1,3,2-dithiaphospholanes

form weak complexes with donor solvents, as indicated by the

NMR data (e.g. the ¹³C NMR spectra of 21 in Fig. 4). It takes

20 h at 90 °C for a [D₈]toluene solution to convert 22 into 8b

and i-PrPBr₂by reaction with an excess of PBr₃.

Using 1,1-bis(dichlorophosphino)methane in the reaction

with 4, the product distribution is markedly dependent on the

ratio of the starting materials (Scheme 8, Fig. 5 and Tables 2

and 3). After warming the reaction mixture with an excess of

the phosphorus dichloride to r.t., the formation of 27 and 28

is observed, and a third product 29 is also present. The latter

could be crystallized at −30 °C and identified by X-ray struc-

tural analysis. The 14-membered macrocycle 29 can be con-

sidered as a dimer of 27. When two equivalents of 4 are used,

the expected product 28 is formed together with yet another

dimer, for which we propose the structure 30 on the basis of

NMR data.

phase structures of all other products were optimised by calcu-

lations at the B3LYP/6-311+G(d,p) level of theory.³³As

expected, the agreement with direct structural evidence for the

solid state is reasonably good (Table 5), since appreciable

intermolecular interactions in the solid state appeared to be

negligible. It turned out that the 1,3,2-dithiaphospholanes

studied here adopt either the conformation

A or A′

(Scheme 10) depending on the nature of the substituent at

phosphorus.

Because of repulsive contacts with the rigid carborane skele-

ton, a bulky substituent R (e.g. R = t-Bu, or NEt₂) will prefer

the equatorial position (A′), and therefore, the axial space will

be filled by the lone pair of electrons at phosphorus, although

this is not favoured in general, again due to repulsive inter-

actions. Smaller substituents (e.g. R = H, CH₂-R′, or the halo-

gens) are accommodated in the axial position (A) leaving the

equatorial space for the lone pair of electrons, the usual enve-

lope conformation of phospholanes. This conformation is also

preferred for the OEt group (17) or the N(H)benzyl group (15).

In the case of the latter, the orthogonality of the orientations

of lone pair of electrons at nitrogen and phosphorus is poss-

ible, since the NH unit requires little space and is tolerated in

the axial position, in contrast with the NEt moiety of the NEt₂

group in 16. In 16, a minimum of energy is achieved with the

NEt₂group in equatorial position and orthogonal orientations

Similar results were obtained, when we studied the reaction

of 4 with 1,2-bis(dichlorophosphino)ethane (Scheme 9 and

Tables 2 and 3). However, there was no evidence for a macro-

cyclic dimer, analogous to 29, of the monomer 31. Again, the

structures of the dimer 33 and 34 follow from NMR data (e.g.,

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Fig. 2 NMR spectra of the 4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphospholane 11 (in [D₈]toluene, at 23 °C), showing long range or

through-space ¹H-¹H and ³¹P-¹H spin–spin coupling, and assignment of ¹¹B and ¹H(BH) NMR signals. (A) 500.13 MHz ¹H NMR spectrum. (B)

500.13 MHz ¹H{³¹P} NMR spectrum. (C) 202.5 MHz ³¹P NMR spectrum. The isotope-induced chemical shift ¹Δ^32/34S(³¹P)²⁷is observed. (D) 202.5 MHz

³¹P{¹H} NMR spectrum with ¹H broad-band decoupling. (E) 202.5 MHz ³¹P{¹H} NMR spectrum with selective decoupling of ¹H at 2.55 ppm. (F)

500.13 MHz ¹H{¹¹B} NMR spectrum of 11 (in [D₈]toluene, at 23 °C), assigned by selective ¹H{¹¹B} experiments. (G) 160.5 MHz ¹¹B{¹H} NMR spectrum

of 11 (in [D₈]toluene, at 23 °C) with side product 9 (marked by asterisks). (H) Stick diagram of calcd ¹¹B NMR signals of 11.

Table 1 ¹³C and ²⁹Si NMR data^aof the ortho-carborane derivatives 1, 4, 13 and 14

Solvent

CD₂Cl₂

δ

¹³C [C(carb)]

Other δ¹³C

1(Et₂O)

94.0

15.0 (CH₃from Et₂O)

66.6 (OCH₂from Et₂O)

4.9 (57.6)

6.2 (57.6)

—

(h_1/2≈ 35 Hz)

84.4 {−8.8}

84.5 {−8.8}

93.6

4

[D₈]toluene

CD₂Cl₂

[D₈]toluene

δ

²⁹Si: 69.3

²⁹Si: 70.1 (57.6)

¹⁹F: −136.4

¹¹B: 60.4

13

14

84.2

—

^aCoupling constants ¹J(²⁹Si,¹³C) ( 0.5 Hz) are given in parentheses, isotope-induced chemical shifts ¹Δ^10/11B[¹³C(carb)]³²in ppb are given in

braces, 0.5 ppb; and the negative sign denotes a shift of the NMR signal of the heavy isotopomer to lower frequency.

of the lone pairs of electrons (Fig. 3). The preference of A or A′ latter are known to be sensitive to the orientation of the lone

is predicted by relative energies given by the calculations and pair of electrons at phosphorus and the S–C bond vector.³⁴

supported by the experimental and calculated NMR data, in For conformation A, calculations give positive values for

particular by the chemical shifts δ³¹P (Fig. 6, Table 4), δ¹³- ²J(³¹P,S,¹³C) of ca. +12 4 Hz whereas for A′, all these values

C(carborane) and the coupling constants ²J(³¹P,¹³C_carb). The are close to zero (Table 2).

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Scheme 6 Synthesis of 2-diethylamino- and 2-ethoxy-1,3,2-dithiaphospholanes.

Apparently, the five-membered ring in the 1,3,2-dithiaphos-

pholanes is strained, although less than that in the corres-

ponding 1,3,2-dioxaphospholanes, because of the longer P–S

and C–S distances. Most of the organo-substituted derivatives

tend to escape this strain by dimerisation. This is confirmed

by the calculations, indicating little relative stabilisation of the

dimer for R = H (1.8 kcal mol⁻¹; dimer experimentally not

observed), somewhat more for R = Ph (2.6 kcal mol⁻¹; see 25

and Fig. 4), R = i-Pr (4.8 kcal mol⁻¹; see 22), and strikingly for

R = t-Bu (15.0 kcal mol⁻¹; see 6). A novel type of such a dimer

is the macrocycle 29, where we find in a monomer–dimer equi-

librium, an unusual 14-membered ring.

X-Ray analyses

The molecular structure of the sulfide 7(S) is shown in Fig. 7.

Intermolecular interactions appear to be negligible. Bond

angles and distances are in the normal range, the PvS bond

being shorter than the P–S bonds.³⁵The five-membered ring is

folded at the sulfur atoms (31.3°), and the t-Bu group is found

in an equatorial position.

The dimer 6 (Fig. 8) shows a structure which is rather

similar to that of the corresponding oxygen analogues.¹⁹The

four sulfur atoms form a plane (mean deviation 0.9 pm), and

the two phosphorus atoms are both shifted to the same

Fig. 3 125.8 MHz ¹³C(carborane) NMR spectra of 15, 16, and 17 (in

[D₈]toluene, at 23 °C).

Scheme 7 Reactions of the silane 4 with various organophosphorus dihalides.

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Table 3 ¹³C and ³¹P NMR data^aof the ortho-carborane derivatives (S₂PR-dimer)

Dimer (exp.)

Dimer (calcd)

¹³C[C(carb)]

R

Solvent

δ

¹³C[C(carb)]

²J(³¹P,¹³C_carb

)

Other δ¹³C

δ

³¹P

δ

³¹P

H

100.9^b

102.1

75.7

170.1

i-Pr (22)

[D₈]toluene

CD₂Cl₂

89.7 {−10.5}

89.7

27.6

27.7

28.8

28.6

27.0

18.7 (16.8)

34.5 (25.0)

19.2 (16.8)

35.0 (24.8)

27.1 (16.6)

40.1 (26.5)

27.1 (16.5)

40.5 (26.4)

21.4

108.7

109.7

119.5

120.1

88.1

t-Bu (6)

CD₂Cl₂

90.3 {−9.9}

91.2 {−9.9}

90.7

103.4

193.9

[D₈]thf

(3,5-Me₂-C₆H₃)-CH₂- (23)

[D₈]thf

42.0(27.0)

129.0 (6.1) C_o

130.1 (4.4) C_p

133.9 (9.4) C_i

139.3 (3.3) C_m

25.7 (1.2)

26.7 (11.9)

29.2 (15.0)

43.7 (26.1)

129.7 (5.4) C_m

131.3 (21.8) C_o

131.3 (1.0) C_p

133.7 (29.9) C_i

Cy (24)

Ph (25)

[D₈]toluene

CD₂Cl₂

90.1

27.8

30.7

103.1

88.6

88.9 {−9.6}

106.9

103.9

203.7

226.4

[(C₂B₁₀S₂PCl)₂CH₂]₂(29)

(C₂B₁₀S₂PCH₂)₂(PS₂C₂B₁₀)₂(30)

[D₈]toluene

CD₂Cl₂

147.4

87.6

91.4 {−7.9}

88.0

30.3

10.0

28.0

10.5

43.0

(74.8) (39.3)

30.5

(30.5) (20.1)

32.2

85.8 <101.1>

120.5 <101.1>

93.7 <20.1>

128.3 <20.1>

(C₂B₁₀S₂PCH₂CH₂)₂(PS₂C₂B₁₀)₂(33)

CD₂Cl₂

91.4

(57.1) (12.7)

(C₂B₁₀S₂PCH₂–)₄(34)

CD₂Cl₂

92.5

direction out of this plane by 120.5 and 121.4 pm. There is (R = t-Bu). Starting from bis(dichlorophosphino)alkanes, novel

hardly any diﬀerence in the P–S bond lengths in 6 when com- macrocyclic dimers are accessible and even polymacrocyclic

pared with those in 7(S), where the phosphorus had been oxi- systems can be formed. The studies of both formation and reac-

dised. An inspection of the ten-membered ring shows that there tivity of the novel 1,3,2-dithiaphospholanes is greatly aided by

is very little space left at the phosphorus atoms to use their application of multinuclear magnetic resonance methods (¹H,

donor capability, as a result of the carborane cages. However, ¹¹B, ¹³C, ¹⁵N, ²⁹Si, and ³¹P NMR) in combination with DFT cal-

the sulfur atoms may become engaged in coordinative inter- culations to obtain the optimised gas phase geometries and

actions, which might lead to ring opening and rearrangements.

The most striking feature of the other macrocyclic dimer 29

(Fig. 9) is the 14-membered ring. There are few examples of

such rings without coordination to a metal,^36,37and there is

none in which sulfur and phosphorus are present. Again the

four sulfur atoms form a plane, and the four phosphorus

NMR parameters for comparison with experimental data.

Experimental section

General

atoms are pairwise with diﬀerent configurations symmetrically All syntheses and the handling of the samples were carried out

above and below that plane.

observing necessary precautions to exclude traces of air and

moisture. Carefully dried solvents and oven-dried glassware

were used throughout. CD₂Cl₂was distilled over CaH₂under

an atmosphere of argon. All other solvents were distilled from

Na metal under an atmosphere of argon. The 1,2-dilithiated

Conclusions

The rigid annelated carborane skeleton in the 1,3,2-dithiaphos- carborane [(1,2-C₂B₁₀H₁₀)Li₂](2Et₂O) was prepared as

pholanes studied here contributes markedly to the strain in the described.²⁴Other starting materials were purchased from

five-membered rings. Thus, bulky substituents at phosphorus KatChem (ortho-carborane), MCAT GmbH (3,5-dimethyl-

can be forced into the equatorial position, and the organo-sub- benzylphosphorus dibromide), Aldrich [butyllithium (1.6 M in

stituted derivatives tend to dimerise reversibly or irreversibly hexane), PCl₃(99.999%), PBr₃(>99.99%), PI₃(99%), i-PrPCl₂

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Fig. 4 (A) 125.8 MHz ¹³C{¹H} NMR spectrum of 2-phenyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphospholane 21 (in [D₈]toluene, at

23 °C). (B) 125.8 MHz ¹³C{¹H} NMR spectrum of 2-phenyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphospholane 21 (in [D₈]thf, at

23 °C); note the markedly diﬀerent δ¹³C values and slightly diﬀerent coupling constants. (C) For comparison with the monomer, the 125.8 MHz ¹³C

{¹H} NMR spectrum of the dimer, 2,7-diphenyl-4,5,9,10-bis[1,2-dicarba-closo-dodecaborano(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane 25 (in

CD₂Cl₂, at 23 °C), is shown. The observed splitting of the ¹³C(carborane) NMR signals, in addition to ²J(³¹P,¹³C), by isotope-induced chemical shifts

¹Δ^10/11B(¹³C) is typical of icosahedral carboranes.³²

(97%), t-BuPCl₂(97%), PhPCl₂(97%), EtOPCl₂(98%), Et₂NPCl₂(CD₂Cl₂) = 53.8, (C₆D₅CD₃) = 20.4, (C₄D₈O) = 25.4 ( 0.1); δ²⁹Si =

(97%), CyPCl₂(95%), 1,1-bis(dichlorophosphino)methane 0 ( 0.1) for Ξ(²⁹Si) = 19.867184 MHz]; external BF₃-OEt₂[d¹¹B =

(95%), 1,2-bis(dichlorophosphino)ethane, BBr₃(1.0

M

in 0 ( 0.3) for X(¹¹B) = 32.083971 MHz], neat MeNO₂[δ¹⁵N = 0 for

hexane)], Acros [Bu₃SnH (97%), SbF₃(98%)], and Fluka Ξ(¹⁵N) = 10.136767 MHz], neat Me₂Se [δ⁷⁷Se = 0 ( 0.1) for

[PhCH₂N(H)SiMe₃(>97%)]. Most syntheses were carried out on Ξ(⁷⁷Se) = 19.071523 MHz], and external aqueous H₃PO₄(85%)

a small scale suﬃcient for NMR studies. Because of the small [δ³¹P = 0 for X(³¹P) = 40.480747 MHz]. Assignments of H and

1

scale, the sensitivity to hydrolysis, and the multiple reaction ¹¹B NMR signals are based on H{¹¹B} selective heteronuclear

1

pathways, it proved diﬃcult to obtain analytically pure decoupling experiments. Mass spectra (EI, 70 eV): Finnigan MAT

1

materials. NMR measurements: Bruker DRX 500: H, ¹¹B, ¹³C, 8500 with direct inlet (data for ¹²C, H, ¹¹B, ³¹P, ³²S, and ⁸⁰Se).

³¹P, ⁷⁷Se, ¹⁵N, and ²⁹Si NMR [refocused INEPT³⁸based on Melting points (uncorrected) were determined using a Büchi

¹J(¹⁵N,¹H) = 80 Hz and ²J(²⁹Si,¹H) = 6–7 Hz, respectively]; Varian 510 melting point apparatus. Combustion analyses proved unre-

INOVA 400: ¹H, ¹¹B, ³¹P NMR; chemical shifts are given relative liable and irreproducible, possibly because of critical experi-

to Me₄Si [δ¹H (CHDCl₂) = 5.33, (C₆D₅CD₂H) = 2.08 ( 0.01); δ¹³C mental conditions, e.g. caused by formation of boron carbides.

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Scheme 8 Reactions of 4 with 1,1-bis(dichlorophosphino)methane.

Computational methods

Li₂](2Et₂O) (1437 mg, 4.72 mmol) was taken up in Et₂O

(20 mL); the suspension was cooled to 0 °C and degassed

All quantum chemical calculations were carried out using the elemental sulfur (303 mg, 9.44 mmol) was added. The reaction

Gaussian 09 program package.³⁹Optimised geometries at the mixture was stirred for 18 h at room temperature (the for-

B3LYP/6-311+G(d.p) level of theory³³were found to be minima mation of a yellowish oily suspension was observed) and Et₂O

by the absence of imaginary frequencies. NMR parameters were (30 mL) was added. The solution was cooled to −30 °C, and

calculated^40,41at the same level of theory. Calculated chemical Me₂SiCl₂(609 mg, 0.57 mL, 4.72 mmol) was injected slowly

shifts δ¹³C, δ³¹P and δ¹¹B were converted by δ¹³C (calcd) = σ(¹³C, (30 min) through a syringe. After stirring the reaction mixture

TMS) − σ(¹³C), with σ(¹³C, TMS) = +181 and [δ¹³C (TMS) = 0], ³¹

P

for 1 h at room temperature, insoluble materials were sepa-

(calcd) = σ(³¹P, P(OMe)₃) − σ(³¹P) + 138; with σ(³¹P, P(OMe)₃) = rated by centrifugation, and the clear liquid was collected.

159.8 ppm [δ³¹P = 138 and δ³¹P (aqueous H₃PO₄(85%) = 0] and Volatile materials were removed in a vacuum, the remaining

δ¹¹B (calcd) = σ(¹¹B) − σ(¹¹B, B₂H₆), with σ(¹¹B, B₂H₆) = +84.1 solid was dissolved in Et₂O (15 mL), insoluble materials were

[δ¹¹B (B₂H₆) = 18 and δ¹¹B (BF₃-OEt₂) = 0].

Dilithium

[(1,2-C₂B₁₀H₁₀)S₂Li₂](Et₂O)

separated by centrifugation, the clear liquid was collected, and

1,2-dicarba-closo-dodecaborane-1,2-dithiolate the volatile materials were removed in a vacuum. Hexane

(1). Freshly prepared [(1,2- (5 mL) was added to the remaining solid, and the residue was

C₂B₁₀H₁₀)Li₂](2Et₂O) (1229 mg, 4.04 mmol) was taken up in dried in a vacuum to give 4 (1112 mg, 89%) as a yellowish

Et₂O (10 mL) and degassed elemental sulfur (259 mg, solid; m.p. 75–80 °C.

8.08 mmol) was added. The reaction mixture was stirred at

¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 0.84 [s, 6H,

r.t. for 18 h. The formation of an oily phase was observed which CH₃Si, ²J(²⁹Si,¹H) = 7.3 Hz], 2.07 [br. s, 2H, HB for δ(¹¹B) =

was separated using a centrifuge. The supernatant liquid −6.6 ppm], 2.29 [br. s, 2H, HB for δ(¹¹B) = −7.6 ppm], 2.52 [br. s,

was decanted and the residue after centrifugation was dried in 4H, HB for δ(¹¹B) = −9.0 ppm], 2.60 [br. s, 2H, HB for δ(¹¹B) =

a vacuum to give 527 mg (44%) of 1 as a yellowish powder.

−3.2 ppm]. ¹¹B{¹H} NMR (160.5 MHz; CD₂Cl₂; 25 °C): δ −9.0

¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 1.38, 3.79 (t, q, (4B, B), −7.6 (2B), −6.6 (2B), −3.2 (2B). ¹¹B NMR (160.5 MHz;

≈10H, OEt₂), 1.92 (br. s, 2H, HB), 2.00 (br. s, 2H, HB), 2.26 (br. CD₂Cl₂; 25 °C): δ −9.0 [d, ¹J(¹¹B,¹H) = 169 Hz, 4B], −7.6 [d,

s, 2H, HB), 2.52 (br. m, 4H, HB). ¹¹B{¹H} NMR (160.5 MHz; ¹J(¹¹B,¹H) = 160 Hz, 2B], −6.6 [d, ¹J(¹¹B,¹H) = 155 Hz, 2B], −3.2

1

CD₂Cl₂; 25 °C): δ −10.3, −8.5 (br. s, br. s, 10B).

[d, J(¹¹B,¹H) = 180 Hz, 2B]. ¹H{¹¹B} NMR (500.13 MHz; [D₈]-

2

2,2-Dimethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

toluene; 25 °C): δ 0.13 [s, 6H, CH₃Si, J(²⁹Si,¹H) = 7.2 Hz], 2.56

dithiasilacyclopentane (4). Freshly prepared [(1,2-C₂B₁₀H₁₀)- [br. s, 2H, HB for δ(¹¹B) = −6.0 ppm], 2.65 [br. s, 2H, HB for

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Fig. 5 202.5 MHz ³¹P{¹H} and 125.8 MHz ¹³C{¹H} NMR spectra (carborane regions) of the reaction solutions obtained from the reaction of 4 with

1,1-bis(dichlorophosphino)methane. (A) The mixture of 27, 28, 29 and 1,1-bis(dichlorophosphino)methane together with unidentiﬁed intermediates

(marked by asterisks) from the reaction of 4 with excess of 1,1-bis(dichlorophosphino)methane (after 20 h at r.t. in [D₈]toluene). (B) The mixture of

28 and 30 from the reaction of 4 with 1,1-bis-(dichlorophosphino)methane (ratio 2 : 1; after 20 h at r.t. in CD₂Cl₂). Note again (see Fig. 4) the splitting

due to isotope-induced chemical shifts ¹Δ^10/11B(¹³C)³²and the virtual triplet for the ¹³C(carborane) NMR signals of 28. Exact simulation of this multi-

plet is diﬃcult, since the isotope-induced chemical shifts ¹Δ^10/11B(¹³C) distort line shapes and intensities.

δ(¹¹B) = −3.1 ppm], 2.70 [br. s, 2H, HB for δ(¹¹B) = −7.2 ppm], Reaction of 1 with t-BuPCl₂

2.78 [br. s, 4H, HB for δ(¹¹B) = −8.7 ppm]. ¹¹B{¹H} NMR

(160.5 MHz; [D₈]toluene; 25 °C): δ −8.7 (4B, B), −7.2 (2B), −6.1

(2B), −3.1 (2B). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C): 1,3,2-dithiaphospholane (5). Freshly prepared [(1,2-C₂B₁₀H₁₀)-

δ −8.7 [d, ¹J(¹¹B,¹H) = 168 Hz, 4B], −7.2 [d, ¹J(¹¹B,¹H) = 161 Hz, S₂Li₂](Et₂O)

(423 mg, 1.44 mmol) was dissolved in

2B], −6.1 [d, J(¹¹B,¹H) = 165 Hz, 2B], −3.1 [d, J(¹¹B,¹H) = 180 toluene (5 mL) and volatile materials were removed in a

2-(1,1-Dimethylethyl)-4,5-[1,2-dicarba-closo-dodecaborano(12)]-

1

Hz, 2B].

vacuum. The remaining solid was taken up in toluene (20 mL);

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Scheme 9 Reactions of 4 with 1,2-bis(dichlorophosphino)ethane.

the solution was cooled to −30 °C, and a solution of t-BuPCl₂

(228 mg, 1.44 mmol) in toluene (5 mL) was added. After stir-

ring the reaction mixture for 1 h at r.t., insoluble materials

were separated by centrifugation, and the clear liquid was col-

lected. Volatile materials were removed in a vacuum to

give 355 mg of the mixture containing 5 (>95%) together

with 7(S) (<5%) as a white solid. After 10 days in [D₈]toluene

at r.t., the mixture contained 5 (60%) and 7(S) (40%). After

30 min in [D₈]thf at r.t., the mixture contained 6 (95%) and

7(S) (5%).

Scheme 10 Likely conformations of 1,3,2-dithiaphospholanes bearing

the substituent at phosphorus either in axial (A) or in equatorial position

(A’).

¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.75 [d,

3

9H, CH₃, J(³¹P,¹H) = 13.1 Hz], 2.62 [br. s, 2H, HB for δ(¹¹B) =

Fig. 6 Comparison of calcd and exp. chemical shifts δ³¹P NMR. Data pairs taken from Table 4.

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CH₃, ³J(³¹P,¹H) = 23.3 Hz)], 2.56 [br. s, 1H, HB for δ(¹¹B) =

−9.9 ppm], 2.59 [br. s, 4H, HB for δ(¹¹B) = −2.6, −5.4 ppm],

2.69 [br. s, 3H, HB for δ(¹¹B) = −6.8, −8.6 ppm], 2.75 [br. s, 1H,

HB for δ(¹¹B) = −6.8 ppm], 3.61 [br. s, 1H, HB for δ(¹¹B) =

−6.8 ppm]. ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C):

δ −9.9 (1B), −8.6 (2B), −6.8 (3B), −5.4 (2B), −2.6 (2B). EI-MS

(70 eV) for C₆H₁₉B₁₀PS₃(326.5): m/z = 326 ([M⁺], 10%),

Table 4 Experimental and calculated δ³¹P NMR chemical shifts of the

ortho-carborane derivatives (S₂PR-monomer and S₂PR-dimer)

δ

³¹P (exp), ppm

δ

³¹P (calcd), ppm

B

₁₀H₁₀C₂S₂PR (monomer):

H (11)

50.4

97.3 (A)

F (12)

Cl (8a)

Br (8b)

OEt (17)

NEt₂(16)

N(H)CH₂Ph (15)

t-Bu (5)

i-Pr (18)

CH₂(3,5-Me₂-C₆H₃) (19)

Ph (21)

CH₂PCl₂(27)

[C₂B₁₀S₂P]₂CH₂(28)

CH₂CH₂PCl₂(31)

(C₂B₁₀S₂PCH₂−)₂(32)

243.2

219.8

221.1

216.7

186.7

161.3

178.4

134.9

127.1

121.3

119.8

123.7

130.7

129.4

331.8 (A)

333.8 (A)

351.8 (A)

294.7 (A)

254.9 (A′)

214.2 (A)

260.0 (A′)

212.4 (A)

201.5 (A)

196.0 (A)

188.7 (A)

191.5 (A)

200.6 (A)

201.5 (A)

+

270 ([M⁺− C₄H₁₀], 5), 237 ([M⁺− S − C₄H₉], 10), 57 ([C₄H₉],

100).

2-(1,1-Dimethylethyl)-2-selenide-4,5-[1,2-dicarba-closo-dode-

caborano(12)]-1,3,2-dithiaphospholane [7(Se)]. About 50 mg of

5 [with 7(S) (5%)] was dissolved in CD₂Cl₂(0.6 mL) and added

to an excess of dry and degassed elemental selenium (ca.

20 mg). The progress of the reaction was monitored by ³¹P

NMR spectroscopy. After 3 h at 50 °C, the mixture contained 5

(50%), 7(S) (15%), 7(Se) (30%) and 6 (5%) (see Fig. 1). After

24 h at 50 °C, the mixture contained 7(S) (20%) and 7(Se)

(80%) (from ³¹P NMR).

[B₁₀H₁₀C₂S₂PR]₂(dimer):

t-Bu (6)

i-Pr (22)

Ph (25)

[(C₂B₁₀S₂PCl)₂CH₂]₂(29)

119.5

108.7

88.6

193.9

170.1

203.7

226.4

¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 1.43 [d, 9H,

CH₃, ³J(³¹P,¹H) = 23.9 Hz], 2.19 [br. s, 2H, HB for δ(¹¹B) =

−5.8 ppm], 2.44 [br. s, 1H, HB for δ(¹¹B) = −6.6 ppm], 2.48 [br.

s, 3H, HB for δ(¹¹B) = −7.2, −10.1 ppm], 2.59 [br. s, 2H, HB for

δ(¹¹B) = −8.7 ppm], 2.83 [br. s, 1H, HB for δ(¹¹B) = −2.3 ppm],

3.57 [br. s, 1H, HB for δ(¹¹B) = −7.2 ppm]. ¹¹B{¹H} NMR

(160.5 MHz; CD₂Cl₂; 25 °C): δ −10.1 (2B), −8.7 (2B), −7.2 (2B),

−6.6 (1B), −5.8 (2B), −2.3 (1B). ¹¹B NMR (160.5 MHz; CD₂Cl₂;

147.4

−11.5 ppm], 2.66 [br. s, 1H, HB for δ(¹¹B) = −9.1 ppm], 2.72

[br. s, 2H, HB for δ(¹¹B) = −4.8 ppm], 2.80 [br. s, 1H, HB for

δ(¹¹B) = −4.4 ppm], 2.85 [br. s, 2H, HB for δ(¹¹B) = −7.5 ppm],

2.93 [br. s, 1H, HB for δ(¹¹B) = 2.6 ppm], 3.30 [br. s, 1H, HB for

δ(¹¹B) = −9.5 ppm]. ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene;

25 °C): δ −11.5 (2B), −9.5 (1B), −9.1 (1B), −7.5 (2B), −4.8 (2B),

−4.4 (1B), 2.6 (1B). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C):

δ −11.5 [d, ¹J(¹¹B,¹H) = 164 Hz, 2B], −9.5 (d, 1B), −9.1 [d,

¹J(¹¹B,¹H) = 150 Hz, 1B], −7.5 [d, ¹J(¹¹B,¹H) = 169 Hz, 2B], −4.8

1

25 °C): δ −10.1 [d, J(¹¹B,¹H) = 172 Hz, 2B], −8.7 [d, J(¹¹B,¹H)

= 170 Hz, 2B], −7.2 [d, J(¹¹B,¹H) = 150 Hz, 2B], −6.6 [d, 1B],

1

−5.8 [d, J(¹¹B,¹H) = 150 Hz, 2B], −2.3 [d, J(¹¹B,¹H) = 180 Hz,

1B]. EI-MS (70 eV) for C₆H₁₉B₁₀PS₂Se (373.4): m/z = 374 ([M⁺],

12%), 316 ([M⁺− C₄H₁₀], 2), 237 ([M⁺− Se − C₄H₉], 10),

1

+

57 ([C₄H₉], 100).

1

[d, J(¹¹B,¹H) = 150 Hz, 2B], −4.4 [d, J(¹¹B,¹H) = 152 Hz, 1B],

2,7-Bis(1,1-dimethylethyl)-4,5,9,10-bis[1,2-dicarba-closo-dode-

caborano(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane (6).

2.6 [d, ¹J(¹¹B,¹H) = 186 Hz, 1B].

2-(1,1-Dimethylethyl)-2-sulfide-4,5-[1,2-dicarba-closo-dodeca-

borano(12)]-1,3,2-dithiaphospholane [7(S)]. About 50 mg of 5

[with 7(S) (5%)] was dissolved in CD₂Cl₂(0.6 mL) and added to

an excess of dry and degassed elemental sulfur (ca. 10 mg).

The progress of the reaction was monitored by ³¹P NMR spec-

troscopy. After 24 h at 55 °C, the solution contained 7(S)

(>95%). Transparent colourless crystals of 7(S) for X-ray analy-

sis were grown from CD₂Cl₂solution after 2 weeks at −30 °C;

m.p. 125–128 °C.

Freshly prepared [(1,2-C₂B₁₀H₁₀)S₂Li₂](Et₂O)

1 (502 mg,

1.71 mmol) was taken up in Et₂O (30 mL); the solution was

cooled to −40 °C, and a solution of t-BuPCl₂(271 mg,

1.71 mmol) in toluene (3 mL) was added. After stirring the

reaction mixture for 1 h at r.t., volatile materials were removed

in a vacuum. The remaining solid was dissolved in toluene

(60 mL), insoluble materials were separated by centrifugation,

the clear liquid was collected, volatile materials were removed

in a vacuum to give 6 (449 mg, 89%) as a white solid. Transpar-

ent colourless crystals of 6, suitable for X-ray analysis, were

grown from CD₂Cl₂solution after 1 week at r.t.; m.p.

325–330 °C.

¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 1.42 [d, 9H,

CH₃, ³J(³¹P,¹H) = 23.8 Hz)], 2.19 [br. s, 2H, HB for δ(¹¹B) =

−5.7 ppm], 2.39 [br. s, 1H, HB for δ(¹¹B) = −6.9 ppm], 2.45 [br.

s, 1H, HB for δ(¹¹B) = −7.2 ppm], 2.50 [br. s, 2H, HB for δ(¹¹B) =

−10.0 ppm], 2.58 [br. s, 2H, HB for δ(¹¹B) = −8.7 ppm], 2.76

[br. s, 1H, HB for δ(¹¹B) = −2.5 ppm], 3.39 [br. s, 1H, HB for

δ(¹¹B) = −6.9 ppm]. ¹¹B{¹H} NMR (160.5 MHz; CD₂Cl₂; 25 °C):

δ −10.0 (2B), −8.7 (2B), −7.2 (1B), −6.9 (2B), −5.7 (2B), −2.5 (1B).

¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 1.35 [d, 18H,

CH₃, ³J(³¹P,¹H) = 15.9 Hz], 2.12 [br. s, 2H, HB for δ(¹¹B) =

−9.8 ppm], 2.24 [br. s, 2H, HB for δ(¹¹B) = −8.5 ppm], 2.38 [br. s,

6H, HB for δ(¹¹B) = −3.1, −6.6 ppm], 2.56 [br. s, 8H, HB for

δ(¹¹B) = −9.8 ppm], 3.07 [br. s, 2H, HB for δ(¹¹B) = −9.8 ppm].

¹¹B{¹H} NMR (160.5 MHz; CD₂Cl₂; 25 °C): δ −9.8 (12B), −8.5

(2B), −6.6 (2B), −3.1 (4B). ¹¹B NMR (160.5 MHz; CD₂Cl₂;

25 °C): δ −9.8 [d, ¹J(¹¹B,¹H) = 173 Hz, 12B], −8.5 (2B), −6.6

1

¹¹B NMR (160.5 MHz; CD₂Cl₂; 25 °C): δ −10.0 [d, J(¹¹B,¹H) =

180 Hz, 2B], −8.7 [d, ¹J(¹¹B,¹H) = 177 Hz, 2B], −7.2 [d,

¹J(¹¹B,¹H) = 150 Hz, 1B], −6.9 [d, ¹J(¹¹B,¹H) = 170 Hz, 2B], −5.7

1

[d, J(¹¹B,¹H) = 162 Hz, 2B], −2.5 [d, J(¹¹B,¹H) = 180 Hz, 1B].

1

[d, J(¹¹B,¹H) = 155 Hz, 2B], −3.1 [d, J(¹¹B,¹H) = 147 Hz, 4B].

¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.90 [d, 9H,

EI-MS (70 eV) for C₁₂H₃₈B₂₀P₂S₄(588.9): m/z = 589 ([M⁺], 2%),

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Table 5 Selected bond lengths [pm] and angles [°] of the ortho-carborane derivative 6, 6(calcd), 7(S), 7(S)(calcd), 29 and 29(calcd)

6

6(calcd) 7(S)

7(S)(calcd)

29

29(calcd)

C(1)–S(1)

C(2)–S(2)

C(3)–S(3)

C(4)–S(4)

178.3(7)

178.5(8)

177.9(9)

178.3(9)

179.8

178.0(4)

178.2(5)

180.5

C(1)–S(1)

C(2A)–S(2)

178.3(4)

178.4(4)

179.7

C(1)–C(2)

C(3)–C(4)

175.6(10) 180.7

181.3(11) 180.7

165.2(6)

164.2

C(1)–C(2)

175.1(5)

182.6

S(1)–P(1)

S(2)–P(2)

S(3)–P(1)

S(4)–P(2)

P(1)–C

P(2)–C

P(1)–S(1)–C(1)

P(1)–S(3)–C(3)

P(2)–S(2)–C(2)

P(2)–S(4)–C(4)

S(1)–C(1)–C(2)

S(2)–C(2)–C(1)

S(3)–C(3)–C(4)

S(4)–C(4)–C(3)

S(1)–P(1)–S(3)

S(2)–P(2)–S(4)

S(1)–P(1)–S(2)

S(2)–P(1)–S(3)

S(1)–P(1)–C

S(2)–P–C

213.5(3)

214.1(3)

213.5(3)

214.4(3)

186.6(8)

188.6(9)

103.1(3)

102.8(3)

101.4(3)

103.2(3)

116.7(5)

117.9(5)

114.0(6)

119.3(6)

218.8

191.6

104.6

117.8

213.35(16) 219.7

214.29(17) 219.7

193.49(16) 194.3

S(1)–P(1)

S(2)–P(2)

P(1)–Cl(1)

P(2)–Cl(2)

P(1)–C(3)

P(2)–C(3)

P(1)–S(1)–C(1)

P(2)–S(2)–C(2A)

212.03(15)

212.60(15)

207.86(15)

208.00(15)

185.6(4)

184.6(4)

99.85(14)

100.92(13)

216.3

216.8

213.1

212.9

187.9

188.0

102.1

101.9

185.5(4)

190.2

98.96(15)

98.90(15)

99.6

116.7(3)

116.9(3)

118.1

S(1)–C(1)–C(2)

S(2A)–C(2)–C(1)

117.2(3)

116.7(3)

116.4

117.0

98.39(12) 99.3

98.48(11) 99.3

115.17(7)

99.26(6)

117.10(7)

115.6

99.1

115.7

P(1)–C(3)–P(2)

C(3)–P(1)–Cl(1)

C(3)–P(2)–Cl(2)

117.8(2)

100.62(14)

96.74(13)

121.4

100.7

95.5

99.4(3)

99.7(4)

98.8(3)

99.2(3)

0.02

99.7

104.60(16) 104.7

104.17(16) 104.7

114.60(16) 115.1

S(1)–P(1)–C(3)

S(2)–P(2)–C(3)

S(1)–P(1)–Cl(1)

S(2)–P(2)–Cl(2)

98.13(15)

95.53(14)

102.65(6)

102.63(6)

3.7

96.8

97.2

105.3

102.9

S(3)–P–C

S(4)–P–C

Plane S(1)–C(1)–C(2)–S(2)

0.8

Plane S(1)–C(1)–C(2)–S(2A)

Plane S(3)–C(3)–C(4)–S(4)

0.08

Plane S(2)–C(2A)–C(1A)–S(1A)

Δ (pm)

Plane S(1)–S(2)–S(1A)–S(2A)

3.7

a

̅

Δ (pm)

Plane S(1)–S(2)–S(3)–S(4)

0.9

2.0

0 (Symmetry)

a

̅

Δ (pm)

Plane P(1)–P(2)–P(1A)–P(2A)

a

̅

Δ (pm)

Plane C(5)–P(1)–P(2)–C(9)

Plane S(1)–C(1)–C(2)–S(2A)–

3.76

a

̅

Δ (pm)

S(1A)–C(1A)–C(2A)–S(2)

a

̅

Δ (pm)

Distance of P(1) from the plane 120.5

70.0

Distance of P(1) from the plane

S(1)–C(1)–C(2)–S(2A), (pm)

Distance of P(2A) from the plane

S(1)–C(1)–C(2)–S(2A, (pm)

203.7

194.3

S(1)–S(2)–S(3)–S(4), (pm)

Distance of P(2) from the plane

S(1)–S(2)–S(3)–S(4), (pm)

121.4

Distance of C(3) from the plane

S(1)–S(2)–S(1A)–S(2A), (pm)

185.3

^aMean deviation from plane.

532 ([M⁺− C₄H₉], 10), 295 ([M/2⁺], 10), 237 ([M/2⁺− C₄H₉], 15),

+

190 (3), 147 (5), 57 ([C₄H₉], 100).

Reactions of 4 with PX₃

2-Chloro-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

dithiaphospholane (8a), 1,2-bis{(4,5-[1,2-dicarba-closo-dodeca-

borano(12)]-1,3,2-dithiaphospholan-2-yl)thio}-1,2-dicarba-

closo-dodecaborane(12) (9), and 1-{4,5-[1,2-dicarba-closo-dode-

caborano(12)]-1,3,2-dithiaphospholan-2-yl}thio-2-mercapto-1,2-

dicarba-closo-dodecaborane(12) (10). A solution of 4 (105 mg,

0.40 mmol) in [D₈]toluene (0.6 mL) was cooled to −30 °C and

PCl₃(0.035 mL, 0.40 mmol) was added through a micro-

syringe. The progress of the reaction was monitored by ³¹P and

²⁹Si NMR spectroscopy. After 20 h at r.t., the mixture contained

8a (80%) and several side products 9 (ca. 5%) and 10 (ca. 15%)

together with Me₂SiCl₂and PCl₃. Volatile materials were

Fig. 7 ORTEP plot (50% probability; hydrogen atoms are omitted for

clarity) of the molecular structure of 2-(1,1-dimethylethyl)-2-sulﬁde-

4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphospholane 7(S)

(for selected distances and angles see Table 5).

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Fig. 8 ORTEP plots for diﬀerent views (50% probability; hydrogen atoms are omitted for clarity) of the molecular structure of 2,7-bis(1,1-dimethyl-

ethyl)-4,5,9,10-bis[1,2-dicarba-closo-dodecaborano(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane

6 (for selected distances and angles see

Table 5).

Fig. 9 ORTEP plot of two views (50% probability; hydrogen atoms are omitted for clarity) of the molecular structure of 2,4,9,11-tetrachloro-

6,7,13,14-bis[1,2-dicarba-closo-dodecaborano(12)]-2,4,9,11-tetraphospha-1,5,8,12-tetrathiacyclotetradecane 29 (toluene is omitted for clarity) (for

selected distances and angles see Table 5). Along the c-direction the structure consists of alternating layers of 29 and layers of toluene.

removed in a vacuum (1 h, 8 × 10⁻³Torr) to give 8a (75%) as a (1B), −7.0 (3B), −4.4 (1B), −0.4 (1B). ¹¹B NMR (160.5 MHz;

white oil together with side products 9 (ca. 15%), 10 (ca. 10%) CD₂Cl₂; 25 °C): δ −11.2 [d, ¹J(¹¹B,¹H) = 166 Hz, 2B], −9.0 [d,

and B₁₀H₁₀C₂(SH)₂. This mixture in [D₈]toluene was heated for ¹J(¹¹B,¹H) = 167 Hz, 2B], −8.6 (d, 1B), −7.0 [d, ¹J(¹¹B,¹H) =

20 h at 70 °C, volatile materials were removed in a vacuum to 157 Hz, 3B], −4.4 [d, ¹J(¹¹B,¹H) = 155 Hz, 1B], −0.4 [d,

give the mixture of 8a (75%) and side products 9 (ca. 20%) and ¹J(¹¹B,¹H) = 185 Hz, 1B].

10 (<5%).

2-Bromo-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

8a: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.49 dithiaphospholane (8b). A solution of 4 (55.3 mg, 0.21 mmol)

[br. s, 5H, HB for δ(¹¹B) = −0.4, −7.0, −11.2 ppm], 2.62 [br. s, in [D₈]toluene (0.6 mL) was cooled to −30 °C and PBr₃

2H, HB for δ(¹¹B) = −9.0 ppm], 2.67 [br. s, 1H, HB for δ(¹¹B) = (0.020 mL, 0.21 mmol) was added through a microsyringe. The

−7.0 ppm], 2.70 [br. s, 1H, HB for δ(¹¹B) = −4.4 ppm], 3.25 progress of the reaction was monitored by ³¹P and ²⁹Si NMR

[br. s, 1H, HB for δ(¹¹B)

=

−8.6 ppm]. ¹¹B{¹H} NMR spectroscopy. After 20 h at r.t., the solution contained 8b

(160.5 MHz; [D₈]toluene; 25 °C): δ −11.2 (2B), −9.0 (2B), −8.6 together with Me₂SiBr₂and PBr₃. Volatile materials were

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removed in a vacuum (2 h, 8 × 10⁻³Torr) to give 8b (90%) as a −5.2 [d, ¹J(¹¹B,¹H) = 150 Hz, 2B^9,12], −3.5 [d, ¹J(¹¹B,¹H) =

white oil together with side product 9 (ca. 5–10%).

152 Hz, 1B¹⁰], 2.2 [d, ¹J(¹¹B,¹H) = 190 Hz, 1B⁶]. For comparison:

8b: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.46 ¹¹B(calcd): δ −15.7 (1B, B³), −14.0 (2B, B^5,11), −10.4 (1B, B⁸),

[br. s, 2H, HB for δ(¹¹B) = −11.1 ppm], 2.51 [br. s, 3H, HB for −8.7 (2B, B^4,7), −4.7 (2B, B^9,12), −3.0 (1B, B¹⁰), +1.1 (1B, B⁶).

δ(¹¹B) = −0.1, −7.0 ppm], 2.65 [br. s, 2H, HB for δ(¹¹B) =

Reaction of 8a with excess of SbF₃

−8.9 ppm], −2.72 (m, 2H, HB for δ(¹¹B) = −4.3, −7.0 ppm],

3.48 [br. s, 1H, HB for δ(¹¹B) = −10.2 ppm]. ¹¹B{¹H} NMR

2-Fluoro-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithia-

(160.5 MHz; [D₈]toluene; 25 °C): δ −11.1 (2B), −10.2 (1B), −8.9 phospholane (12) and 2-fluoro-4,5-[1,2-dicarba-closo-dode-

(2B), −7.0 (3B), −4.3 (1B), −0.1 (1B). ¹¹B NMR (160.5 MHz; caborano(12)]-1,3,2-dithiastibolane (13). A solution of 8a

CD₂Cl₂; 25 °C): δ −11.1 [d, ¹J(¹¹B,¹H) = 164 Hz, 2B], −10.2 (1B), (0.29 mmol) (with 9 and 10) (from 4 and PCl₃, vide supra) in

1

−8.9 [d, J(¹¹B,¹H) = 169 Hz, 2B], −7.0 [d, J(¹¹B,¹H) = 153 Hz, [D₈]toluene (0.5 mL) was cooled to 0 °C and added to an

3B], −4.3 [d, ¹J(¹¹B,¹H) = 157 Hz, 1B], −0.1 [d, ¹J(¹¹B,¹H) = excess of dry and degassed SbF₃. The progress of the reaction

184 Hz, 1B].

was monitored by ³¹P NMR spectroscopy. The mixture was

2-Iodo-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithia- heated at 50 °C for 5 h, and the suspension was centrifuged to

phospholane (8c). A solution of 4 (82 mg; 0.31 mmol) in [D₈]- separate the excess of SbF₃and other insoluble materials. The

toluene (0.5 mL) was cooled to −30 °C and added to PI₃reaction solution contained 12 (ca. 40%) and 13 (ca. 60%)

(128 mg; 0.31 mmol). The formation of a red solution was together with PF₃, HPF₂, 9 and 10 (from ¹⁹F and ³¹P NMR).

observed. The progress of the reaction was monitored by ¹H,

PF₃: ³¹P NMR (202.5 MHz; [D₈]toluene; 25 °C): 104.3 [q,

³¹P and ²⁹Si NMR spectroscopy. After 2 h at 80 °C, the mixture ¹J(³¹P,¹⁹F) = 1397.3 Hz]. ¹⁹F NMR (376.1 MHz; [D₈]toluene;

contained 8c together with Me₂SiI₂, PI₃and several side pro- 25 °C): δ −37.8 [d, ¹J(³¹P,¹⁹F) = 1397.0 Hz].

1

ducts, among them 9 and B₁₀H₁₀C₂(SH)₂. Volatile materials

HPF₂: H NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 5.33 [dt,

were removed in a vacuum (2 h, 8 × 10⁻³Torr) to give 8b (90%) 1H, PH, J(³¹P,¹H) = 845.2 Hz, J(¹⁹F,¹H) = 116.5 Hz]. ³¹P NMR

1

as

a

yellow solid together with side products

9

and (202.5 MHz; [D₈]toluene; 25 °C): δ −4.3 [dt, ¹J(³¹P,¹⁹F) = 1128.0

1

[B₁₀H₁₀C₂(SH)₂].

Hz, J(³¹P,¹H) = 844.8 Hz]. ¹⁹F NMR (376.1 MHz; [D₈]toluene;

8c: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.44 25 °C): δ −66.0 [dd, J(³¹P,¹⁹F) = 1128.1 Hz, J(¹⁹F,¹H) = 116.8

1

[br. s, 2H, HB for δ(¹¹B) = −11.2 ppm], 2.50 [br. s, 2H, HB for Hz].

δ(¹¹B) = −7.4 ppm], 2.59 [br. s, 1H, HB for δ(¹¹B) = 0.6 ppm],

1,2-Bis{(4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

2.67 [br. s, 2H, HB for δ(¹¹B) = −8.7 ppm], −2.74 [m, 2H, HB dithiaphospholan-2-yl)thio}-1,2-dicarba-closo-dodecaborane-

for δ(¹¹B) = −4.1, −7.4 ppm], 3.79 [br. s, 1H, HB for δ(¹¹B) = (12) (9). A solution of 8a (0.29 mmol) (with 9 and 10) (from 4

−13.2 ppm]. ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C): and PCl₃, vide supra) in CD₂Cl₂(0.5 mL) was cooled to 0 °C

δ −13.2 (1B), −11.2 (2B), −8.7 (2B), −7.4 (3B), −4.1 (1B), 0.6 and added to an excess of dry and degassed SbF₃. The progress

(1B). ¹¹B NMR (160.5 MHz; CD₂Cl₂; 25 °C): δ −13.2 (d, 1B), of the reaction was monitored by ³¹P NMR spectroscopy. The

−11.2 [d, ¹J(¹¹B,¹H) = 164 Hz, 2B], −8.7 [d, ¹J(¹¹B,¹H) = 169 Hz, formation of a white-yellowish powder of 9 was observed.

2B], −7.4 [d, ¹J(¹¹B,¹H) = 153 Hz, 3B], −4.1 [d, ¹J(¹¹B, ¹H) = Insoluble materials were separated by centrifugation, washed

1

157 Hz, 1B], 0.6 [d, J(¹¹B,¹H) = 184 Hz, 1B]. EI-MS (70 eV) for with toluene (0.4 mL), and dried in a vacuum to give 9 as a

C₂H₁₀B₁₀PS₂I (364.2): m/z = 364 ([M⁺], 1%), 237 ([M⁺− I], 100), light yellow solid.

206 ([M⁺− PI], 5).

¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 2.22 [br. s, 6H,

4,5-[1,2-Dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphos- HB for δ(¹¹B) = −6.5, −8.6 ppm], 2.43 [br. s, 2H, HB for δ(¹¹B) =

pholane (11). A solution of 8b (0.17 mmol) (from 4 and PBr₃, −2.2 ppm], 2.46 [br. s, 2H, HB for δ(¹¹B) = −7.4 ppm], 2.49 [br.

vide supra) in [D₈]toluene (0.5 mL) was cooled to −30 °C and s, 8H, HB for δ(¹¹B) = −4.6, −11.6 ppm], 2.56 [br. s, 4H, HB for

Bu₃SnH (495 mg, 0.03 mL, 0.17 mmol) was added through a δ(¹¹B) = −8.6 ppm], 2.69 [br. s, 6H, HB for δ(¹¹B) = 0.0,

microsyringe. The progress of the reaction was monitored by −8.6 ppm], 2.92 [br. s, 2H, HB for δ(¹¹B) = −7.4 ppm]. ¹¹B{¹H}

³¹P NMR spectroscopy. After 30 min at r.t., the mixture con- NMR (160.5 MHz; [D₈]toluene; 25 °C): δ −11.6 (6B), −8.6 (10B),

tained 11 (Fig. 2) together with Bu₃SnBr, 9, 10 and PH₃.

−7.4 (4B), −6.5 (4B), −4.6 (2B), −2.2 (2B), 0.0 (2B). EI-MS (70

11: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.47 eV) for C₆H₃₀B₃₀P₂S₆(681.0): m/z = 681 ([M⁺], <1%), 445 ([M⁺−

[br. s, 2H, HB^5,11for δ(¹¹B) = −12.5 ppm], 2.55 [br. s, 2H, HB³, C₂H₁₀B₁₀S₂P], 100), 237 ([C₂H₁₀B₁₀S₂P], 45).

HB⁸for δ(¹¹B) = −13.8, −9.9 ppm], 2.67 [br. s, 4H, HB^4,7,HB^9,12

2-Bromo-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

for δ(¹¹B) = −7.4, −5.2 ppm], 2.72 [br. s, 1H, HB⁶for δ(¹¹B) = dithiaborolane (14). A solution of 8b (0.20 mmol) (from 4 and

2.2 ppm], 2.79 [br. s, 1H, HB¹⁰for δ(¹¹B) = −3.5 ppm], 5.37 [dd, PBr₃, vide supra) in [D₈]toluene (0.5 mL) was cooled to 0 °C

1H, PH, ¹J(³¹P,¹H) = 203.5 Hz, J(¹H_PH,¹H_B(3)H) = 1.4 Hz]. and BBr₃(0.2 mL of a 1.0 M solution in hexane, 0.20 mmol)

¹H{³¹P} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 5.37 (s, 1H, was added. The mixture was stirred for 1 d at r.t. The solution

PH). ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C): δ −13.8 thus obtained contained 14 (60%), 8b (40%), PBr₃, BBr₃and

(1B³), −12.5 (2B^5,11), −9.9 (1B⁸), −7.4 (2B^4,7), −5.2 (2B^9,12), −3.5 hexane.

(1B¹⁰), 2.2 (1B⁶). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C):

2-(Phenylmethyl)amino-4,5-[1,2-dicarba-closo-dodecaborano-

1

δ −13.8 (d, 1B³), −12.5 [d, J(¹¹B,¹H) = 170 Hz, 2B^5,11], −9.9 [d, (12)]-1,3,2-dithiaphospholane

(15). A

solution

of

8b

1

¹J(¹¹B,¹H) = 156 Hz, 1B⁸], −7.4 [d, J(¹¹B,¹H) = 169 Hz, 2B^4,7], (0.28 mmol) (from 4 and PBr₃, vide supra) in [D₈]toluene

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(0.5 mL) was cooled to 0 °C and PhCH₂N(H)SiMe₃(50 mg, −7.1 ppm], 2.65 [br. s, 2H, HB for δ(¹¹B) = −10.8 ppm], 2.72

0.055 mL, 0.28 mmol) was added through a microsyringe. The [br. s, 2H, HB for δ(¹¹B) = −0.4, −7.1 ppm], 2.76 [br. s, 3H, HB

progress of the reaction was monitored by ³¹P NMR spec- for δ(¹¹B) = −5.0, −9.0 ppm], 2.92 [br. s, 1H, HB for δ(¹¹B) =

3

troscopy. After 2 h at r.t., the mixture contained 15 together −6.3 ppm], 3.16 [dq, 2H, POCH₂, J(¹H,¹H) = 7.0 Hz, ³J(³¹P,¹H)

with Me₃SiBr, 9, and several side products. Volatile materials = 10.7 Hz]. ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C):

were removed in a vacuum (2 h, 8 × 10⁻³Torr) to give 15 δ −10.8 (2B), −9.0 (2B), −7.1 (3B), −6.3 (1B), −5.0 (1B), −0.4

(purity ca. 90%) as a white oil.

(1B). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C): δ −10.8 [d,

¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.54 [br. s, ¹J(¹¹B,¹H) = 168 Hz, 2B], −9.0 [d, ¹J(¹¹B,¹H) = 168 Hz, 2B], −7.1

1H, HB for δ(¹¹B) = −3.1 ppm], 2.60 [br. s, 2H, HB for δ(¹¹B) = [d, J(¹¹B,¹H) = 150 Hz, 3B], −6.3 (d, 1B), −5.0 [d, J(¹¹B,¹H) =

1

−6.3 ppm], 2.74 [br. s, 7H, HB for δ(¹¹B) = −3.1, −6.3, 152 Hz, 1B], −0.4 [d, ¹J(¹¹B,¹H) = 182 Hz, 1B]. EI-MS (70 eV) for

2

3

−9.8 ppm], 2.85 [dt, 1H, NH, J(³¹P,¹H) = 10.4 Hz, J(¹H,¹H) = C₄H₁₅B₁₀OPS₂(282.4): m/z = 282 ([M⁺], 55%), 254 ([M⁺− C₂H₄],

6.9 Hz], 3.62 [dd, 2H, PNCH₂, J(¹H,¹H) = 6.9 Hz, J(³¹P,¹H) = 100), 236 (25).

3

12.3 Hz], 6.78 (m, 1H, Ph), 7.03 (m, 4H, Ph). ¹¹B{¹H} NMR

2-(1-Methylethyl)-4,5-[1,2-dicarba-closo-dodecaborano(12)]-

(160.5 MHz; [D₈]toluene; 25 °C): δ −9.8 (4B), −6.3 (4B), −3.1 1,3,2-dithiaphospholane (18) and 2,7-di(1-methylethyl)-

(2B). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C): δ −9.8 [d, 4,5,9,10-bis[1,2-dicarba-closo-dodecaborano(12)]-2,7-diphospha-

¹J(¹¹B,¹H) = 170 Hz, 4B], −6.3 [d, ¹J(¹¹B,¹H) = 150 Hz, 4B], −3.1 1,3,6,8-tetrathiacyclodecane (22). A solution of 4 (49 mg,

[d, ¹J(¹¹B,¹H) = 185 Hz, 2B]. EI-MS (70 eV) for C₉H₁₈B₁₀NPS₂0.18 mmol) in [D₈]toluene (0.6 mL) was cooled to −30 °C and

(343.5): m/z = 343 ([M⁺], 15%), 237 ([M⁺− NH(CH₂Ph)], 5), i-PrPCl₂(0.022 mL, 0.18 mmol) was added through a micro-

91 (100).

syringe. The progress of the reaction was monitored by ³¹P and

²⁹Si NMR spectroscopy. After 30 min at r.t., the mixture con-

tained 18 together with Me₂SiCl₂. After 2 h at r.t., the mixture

Reactions of 4 with RPX₂

2-Diethylamino-4,5-[1,2-dicarba-closo-dodecaborano(12)]- contained 18 (90%), 22 (10%) and Me₂SiCl₂. Volatile materials

1,3,2-dithiaphospholane (16). A solution of

(53 mg, were removed in a vacuum (1 h, 8 × 10⁻³Torr) to give 22

4

0.20 mmol) in [D₈]toluene (0.6 mL) was cooled to −30 °C and (purity > 90%) as a white solid showing rather low solubility in

Et₂NPCl₂(0.029 mL, 0.20 mmol) was added through a micro- [D₈]toluene. The precipitates were separated by centrifugation

syringe. The progress of the reaction was monitored by ³¹P and and dried in a vacuum to give 22 as a white solid; m.p.

²⁹Si NMR spectroscopy. After 30 min at r.t., the mixture con- 145–150 °C. The dimer 22 was dissolved in [D₈]toluene;

tained 16 together with Me₂SiCl₂. Volatile materials were after 2 d at r.t., the solution contained 18 (20%) and 22

removed in a vacuum (1 h, 8 × 10⁻³Torr) to give 16 (purity ca. (80%).

95%) as a white oil.

¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.59 [t, [dd, 6H, CH₃, ³J(³¹P,¹H) = 21.1 Hz, ³J(¹H,¹H) = 7.0 Hz], 2.28

18: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.59

3

2

3

6H, CH₃, J(¹H,¹H) = 7.2 Hz], 2.62 [br. s, 1H, HB for δ(¹¹B) = [dsep, 1H, PCH, J(³¹P,¹H) = 3.5 Hz, J(¹H,¹H) = 7.0 Hz], 2.59

−9.2 ppm], 2.68 [br. s, 4H, HB for δ(¹¹B) = −4.8, −11.1 ppm], [br. s, 2H, HB for δ(¹¹B) = −6.8 ppm], 2.65 [br. s, 3H, HB for

2.75 [br. s, 1H, HB for δ(¹¹B) = −5.6 ppm], 2.77 [dq, 4H, δ(¹¹B) = −6.8, −10.8 ppm], 2.69 [br. s, 2H, HB for δ(¹¹B) =

PNCH₂, ³J(¹H,¹H) = 7.2 Hz, ³J(³¹P,¹H) = 11.2 Hz], 2.83 [br. s, −9.2 ppm], 2.73 [br. s, 1H, HB for δ(¹¹B) = −6.8 ppm], 2.80 [br.

3H, HB for δ(¹¹B) = −7.1, −8.2 ppm], 3.00 [br. s, 1H, HB for s, 1H, HB for δ(¹¹B) = −4.5 ppm], 2.92 [br. s, 1H, HB for δ(¹¹B)

δ(¹¹B) = 1.4 ppm]. ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; = 0.6 ppm]. ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C):

25 °C): δ −11.1 (2B), −9.2 (1B), −8.2 (2B), −7.1 (1B), −5.6 (1B), δ −10.8 (2B), −9.2 (2B), −6.8 (4B), −4.5 (1B), 0.6 (1B). ¹¹B NMR

−4.8 (2B), 1.4 (1B). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C): (160.5 MHz; [D₈]toluene; 25 °C): δ −10.8 [d, ¹J(¹¹B,¹H) = 168

δ −11.1 [d, ¹J(¹¹B,¹H) = 163 Hz, 2B], −9.2 [d, ¹J(¹¹B,¹H) = Hz, 2B], −9.2 [d, J(¹¹B,¹H) = 164 Hz, 2B], −6.8 [d, J(¹¹B,¹H) =

155 Hz, 1B], −8.2 [d, ¹J(¹¹B,¹H) = 170 Hz, 2B], −7.1 [d, 146 Hz, 4B], −4.5 [d, ¹J(¹¹B,¹H) = 153 Hz, 1B], 0.6 [d, ¹J(¹¹B,¹H)

¹J(¹¹B,¹H) = 156 Hz, 1B], −5.6 [d, ¹J(¹¹B,¹H) = 145 Hz, 1B], −4.8 = 190 Hz, 1B]. ¹H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C):

1

[d, ¹J(¹¹B,¹H) = 145 Hz, 2B], 1.4 [d, ¹J(¹¹B,¹H) = 174 Hz, 1B]. δ 1.10 [dd, 6H, CH₃, J(³¹P,¹H) = 21.4 Hz, J(¹H,¹H) = 7.2 Hz)],

3

EI-MS (70 eV) for C₆H₂₀B₁₀NPS₂(309.4): m/z = 309 ([M⁺], 45%), 2.11 [br. s, 2H, HB for δ(¹¹B) = −7.3 ppm], 2.33 [br. s, 1H, HB

294 ([M⁺− CH₃], 45), 237 ([M⁺− NEt₂], 100).

for δ(¹¹B) = −7.3 ppm], 2.39 [br. s, 1H, HB for δ(¹¹B) =

2-Ethoxy-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2- −4.9 ppm], 2.48 [br. s, 2H, HB for δ(¹¹B) = −11.0 ppm], 2.54

dithiaphospholane (17). A solution of 4 (69.3 mg, 0.26 mmol) [br. s, 2H, HB for δ(¹¹B) = −9.3 ppm], 2.76 [br. s, 1H, HB for

in [D₈]toluene (0.6 mL) was cooled to −30 °C and EtOPCl₂δ(¹¹B) = −7.3 ppm], 2.80 [br. s, 1H, HB for δ(¹¹B) = 0.6 ppm],

(0.030 mL, 0.26 mmol) was added through a microsyringe. The 2.81 [dsep, 1H, PCH, J(³¹P,¹H) = 3.9 Hz, J(¹H,¹H) = 7.2 Hz].

progress of the reaction was monitored by ³¹P and ²⁹Si NMR ¹¹B{¹H} NMR (160.5 MHz; CD₂Cl₂; 25 °C): δ −11.0 (2B), −9.3

spectroscopy. After 30 min at r.t., the mixture contained 17 (2B), −7.3 (4B), −4.9 (1B), 0.6 (1B). ¹¹B NMR (160.5 MHz;

together with Me₂SiCl₂. Volatile materials were removed in a CD₂Cl₂; 25 °C): δ −11.0 [d, ¹J(¹¹B,¹H) = 167 Hz, 2B], −9.3 [d,

vacuum (1 h, 8 × 10⁻³Torr) to give 17 (purity > 95%) as a white ¹J(¹¹B,¹H) = 165 Hz, 2B], −7.3 [d, ¹J(¹¹B,¹H) = 150 Hz, 4B], −4.9

2

3

oil.

[d, ¹J(¹¹B,¹H) = 152 Hz, 1B], 0.6 [d, ¹J(¹¹B,¹H) = 186 Hz, 1B].

22: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.91

¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.76

[t, 3H, CH₃, ³J(¹H,¹H) = 7.0 Hz], 2.54 [br. s, 2H, HB for δ(¹¹B) = [dd, 12H, CH₃, J(³¹P,¹H) = 17.3 Hz, J(¹H,¹H) = 7.0 Hz], 1.68

3

5038 | Dalton Trans., 2014, 43, 5021–5043

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Dalton Transactions

Paper

2

3

[dsep, 2H, PCH, J(³¹P,¹H) = 8.8 Hz, J(¹H,¹H) = 7.0 Hz], 2.24

20: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.58

[br. s, 2H, HB for δ(¹¹B) = −9.4 ppm], 2.64, 2.65 [br. s, br. s, [m, 2H, C(2)H^a], 0.82 [m, 1H, C(4)H^a], 0.88 [m, 2H, C(3)H^a],

2H, 4H, HB for δ(¹¹B) = −9.4 ppm], 2.76 [br. s, 4H, HB for 1.37 [m, 1H, C(4)H^b], 1.44 [m, 4H, C(3)H^b, C(2)H^b], 2.25 [dtt,

δ(¹¹B) = −6.3 ppm], 2.92 [br. s, 6H, HB for δ(¹¹B) = −2.5 ppm], 1H, PC(1)H, ²J(³¹P,¹H) = 3.2 Hz, ³J(¹H,¹H_trans) = 12.3 Hz,

3.25 [br. s, 2H, HB for δ(¹¹B) = −9.4 ppm]. ¹¹B{¹H} NMR ³J(¹H,¹H_cis) = 3.8 Hz], 2.60 [br. s, 2H, HB for δ(¹¹B) = −6.8 ppm],

(160.5 MHz; [D₈]toluene; 25 °C): δ −9.4 (10B), −6.3 (4B), −2.5 2.69 [br. s, 2H, HB for δ(¹¹B) = −10.7 ppm], 2.74 [br. s, 3H, HB

(6B). EI-MS (70 eV) for C₁₀H₃₄B₂₀P₂S₄(560.8): m/z = 519 ([M⁺− for δ(¹¹B) = −6.8, −9.2 ppm], 2.80 [br. s, 2H, HB for δ(¹¹B) =

C₃H₆], 3%), 415 (5), 280 ([M/2⁺], 15), 264 (5), 237 ([M/2⁺

C₃H₇], 15), 208 (40), 43 (100).

−

−4.6, −6.8 ppm], 2.98 [br. s, 1H, HB for δ(¹¹B) = 0.4 ppm].

¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C): δ −10.7 (2B),

2-[3,5-Dimethylphenyl-methyl]-4,5-[1,2-dicarba-closo-dodeca- −9.2 (2B), −6.8 (4B), −4.6 (1B), 0.4 (1B). ¹¹B NMR (160.5 MHz;

borano(12)]-1,3,2-dithiaphospholane (19) and 2,7-bis(3,5- [D₈]toluene; 25 °C): δ −10.7 [d, ¹J(¹¹B,¹H) = 173 Hz, 2B], −9.2 [d,

dimethylphenyl-methyl)-4,5,9,10-bis[1,2-dicarba-closo-dodeca- ¹J(¹¹B,¹H) = 168 Hz, 2B], −6.8 [d, J(¹¹B,¹H) = 152 Hz, 4B], −4.6

1

borano(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane (23). A [d, ¹J(¹¹B,¹H) = 152 Hz, 1B], 0.4 [d, ¹J(¹¹B,¹H) = 195 Hz, 1B]. ¹H

solution of 4 (82 mg, 0.31 mmol) in [D₈]toluene (0.6 mL) was {¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 1.07 [m, 2H, C(2)

cooled to −30 °C and (3,5-Me₂-C₆H₃)CH₂PBr₂(95 mg, H^a], 1.21 [m, 1H, C(4)H^a], 1.33 [m, 2H, C(3)H^a], 1.72 [m, 1H,

0.31 mmol) was added through a microsyringe. The progress C(4)H^b], 1.83 [m, 4H, C(3)H^b, C(2)H^b], 2.11 [br. s, 2H, HB for

of the reaction was monitored by ³¹P and ²⁹Si NMR spec- δ(¹¹B) = −7.3 ppm], 2.34 [br. s, 1H, HB for δ(¹¹B) = −7.3 ppm],

troscopy. After 1 h at r.t., the mixture contained 19 (95%) and 2.42 [br. s, 1H, HB for δ(¹¹B) = −4.9 ppm], 2.47 [br. s, 2H, HB

23 (ca. 5%) together with Me₂SiBr₂. A white powder consisting for δ(¹¹B) = −11.1 ppm], 2.54 [br. s, 2H, HB for δ(¹¹B) =

of products 19 and 23 was formed showing rather low solubi- −9.3 ppm], 2.58 [dtt, 1H, PC(1)H, ²J(³¹P,¹H) = 3.7 Hz,

3

lity in [D₈]toluene. Insoluble solids were separated by centrifu- ³J(¹H,¹H_trans) = 12.2 Hz, J(¹H,¹H_cis) = 3.7 Hz], 2.75 [br. s, 1H,

gation and dried in a vacuum to give a mixture containing 19 HB for δ(¹¹B) = −7.3 ppm], 2.80 [br. s, 1H, HB for δ(¹¹B) =

(90%) and 23 (10%) as a white solid.

0.6 ppm]. ¹¹B{¹H} NMR (160.5 MHz; CD₂Cl₂; 25 °C): δ −11.1

19: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.08 (2B), −9.3 (2B), −7.3 (4B), −4.9 (1B), 0.6 (1B). ¹¹B NMR

(s, 6H, CH₃), 2.56 [br. s, 2H, HB for δ(¹¹B) = −6.7 ppm], 2.63 (160.5 MHz; CD₂Cl₂; 25 °C): δ −11.1 [d, ¹J(¹¹B,¹H) = 173 Hz,

[br. s, 2H, HB for δ(¹¹B) = −10.5 ppm], 2.74 [br. s, 4H, HB for 2B], −9.3 [d, J(¹¹B,¹H) = 162 Hz, 2B], −7.3 [d, J(¹¹B,¹H) = 152

1

δ(¹¹B) = −4.7, −6.7, −9.3 ppm], 2.88 [br. s, 1H, HB for δ(¹¹B) = Hz, 4B], −4.9 [d, J(¹¹B,¹H) = 155 Hz, 1B], 0.6 [d, J(¹¹B,¹H) =

1

0.1 ppm], 2.97 [br. s, 1H, HB for δ(¹¹B) = −6.7 ppm], 3.07 188 Hz, 1B].

2

[d, 2H, PCH₂, J(³¹P,¹H) = 10.3 Hz], 6.51 (s, 2H, CH, Ph), 6.62

24: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 0.94

(s, 1H, CH, Ph). ¹¹B{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C): (m, 6H, CH), 1.08 (m, 4H, CH), 1.43 (m, 2H, CH), 1.54 (m, 4H,

1

δ −10.5 (2B), −9.3 (2B), −6.7 (4B), −4.7 (1B), 0.1 (1B). H NMR CH), 1.66 [m, 2H, PC(1)H], 2.86 (m, 4H, CH), 2.30 [br. s, 2H,

(500.13 MHz; CD₂Cl₂; 25 °C): δ 2.28 (s, 6H, CH₃), 3.63 [d, 2H, HB for δ(¹¹B) = −9.7 ppm], 2.61 [br. s, 2H, HB for δ(¹¹B) =

PCH₂, ²J(³¹P,¹H) = 9.8 Hz], 6.80 (s, 2H, CH, Ph), 6.92 (s, 1H, −9.7 ppm], 2.71 [br. s, 8H, HB for δ(¹¹B) = −9.7 ppm], 2.80 [br.

1

CH, Ph). H NMR (500.13 MHz; [D₈]thf; 25 °C): δ 2.27 (s, 6H, s, 2H, HB for δ(¹¹B) = −6.8 ppm], 2.94 [br. s, 4H, HB for δ(¹¹B)

2

CH₃), 3.71 [d, 2H, PCH₂, J(³¹P,¹H) = 8.7 Hz], 6.84 (s, 2H, CH, = −2.8 ppm], 3.32 [br. s, 2H, HB for δ(¹¹B) = −9.7 ppm]. ¹¹B

Ph), 6.90 (s, 1H, CH, Ph). EI-MS (70 eV) for C₁₁H₂₁B₁₀PS₂{¹H} NMR (160.5 MHz; [D₈]toluene; 25 °C): δ −9.7 (14B), −6.8

(356.4): m/z = 356 ([M⁺− C₉H₁₁], 10%), 119 ([C₉H₁₁⁺], 100).

(2B), −2.8 (4B). EI-MS (70 eV) for C₁₆H₄₂B₂₀P₂S₄(640.9): m/z =

23: ¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 2.30 (s, 12H, 558 ([M⁺− C₆H₁₁], 2%), 320 ([M/2⁺], 30), 237 ([(M/2 − C₆H₁₁)],

2

CH₃), 3.46 [d, 4H, PCH₂, J(³¹P,¹H) = 11.2 Hz], 6.89 (s, 4H, CH, 15), 83 ([C₆H₁₁⁺], 100).

Ph), 6.94 (s, 2H, CH, Ph). EI-MS (70 eV) for C₂₂H₄₂B₂₀P₂S₄

2-Phenyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

dithiaphospholane (21). A solution of 4 (74 mg, 0.28 mmol) in

(713.4): m/z = 595 ([MH⁺− C₉H₁₁], 7%), 119 ([C₉H₁₁⁺], 100).

2-Cyclohexyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2- [D₈]toluene (0.6 mL) was cooled to −30 °C and PhPCl₂

dithiaphospholane (20) and 2,7-dicyclohexyl-4,5,9,10-bis[1,2- (0.038 mL, 0.28 mmol) was added through a microsyringe. The

dicarba-closo-dodecaborano(12)]-2,7-diphospha-1,3,6,8-tetra- progress of the reaction was monitored by ³¹P and ²⁹Si NMR

thiacyclodecane (24). A solution of 4 (48 mg, 0.18 mmol) in spectroscopy. After 30 min at r.t., the mixture contained 21

[D₈]toluene (0.6 mL) was cooled to −30 °C and CyPCl₂together with Me₂SiCl₂. Volatile materials were removed in a

(0.028 mL, 0.18 mmol) was added through a microsyringe. The vacuum (1 h, 8 × 10⁻³Torr) to give 21 (purity ca. 95%) as a

progress of the reaction was monitored by ³¹P and ²⁹Si NMR white oil together with 25 (<5%) and unidentified intermedi-

spectroscopy. After 15 min at r.t., the mixture contained 20 ates. The monomer 21 can be stored for prolonged periods of

(ca. 90%) and 24 (ca. 10%) together with Me₂SiCl₂. A white time in [D₈]toluene at −30 °C.

powder consisting of dimer 24 was formed showing rather

21: ¹H{¹¹B} NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.18

low solubility in [D₈]toluene. After 18 h at r.t., insoluble [br. s, 1H, HB for δ(¹¹B) = −9.1 ppm], 2.42 [br. s, 1H, HB for

solids were separated by centrifugation, and dissolved in δ(¹¹B) = −7.7 ppm], 2.52 [br. s, 2H, HB for δ(¹¹B) = −6.5 ppm],

CD₂Cl₂. The solid floating on top of the solution was collected 2.57 [br. s, 2H, HB for δ(¹¹B) = −9.1 ppm], 2.62 [br. s, 2H, HB

and dried in a vacuum to give 24 as a white powder; m.p. for δ(¹¹B) = −11.3 ppm], 2.78 [br. s, 1H, HB for δ(¹¹B) =

200–205 °C.

−4.5 ppm], 2.98 [br. s, 1H, HB for δ(¹¹B) = 0.6 ppm], 6.92 (m,

Dalton Trans., 2014, 43, 5021–5043 | 5039

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Dalton Transactions

3H, Ph), 7.12 (m, 2H, Ph). ¹¹B{¹H} NMR (160.5 MHz; [D₈]- intermediates (30%) together with Me₂SiCl₂. After 4 days at

toluene; 25 °C): δ −11.3 (2B), −9.1 (3B), −7.7 (1B), −6.5 (2B), r.t., the mixture contained 5 (60%), 6 (35%), unidentified inter-

−4.5 (1B), 0.6 (1B). ¹¹B NMR (160.5 MHz; [D₈]toluene; 25 °C): mediates (5%) together with Me₂SiCl₂. Volatile materials were

δ −11.3 [d, ¹J(¹¹B,¹H) = 166 Hz, 2B], −9.1 [d, ¹J(¹¹B,¹H) = 170 Hz, removed in a vacuum, the residue was dissolved in CD₂Cl₂.

3B], −7.7 (d, 1B), −6.5 [d, ¹J(¹¹B,¹H) = 163 Hz, 2B], −4.5 [d, Transparent colourless crystals of 6 were grown from CD₂Cl₂

¹J(¹¹B,¹H) = 153 Hz, 1B], 0.6 [d, ¹J(¹¹B,¹H) = 175 Hz, 1B]. ¹H{¹¹B} solution after 1 week at r.t.

NMR (500.13 MHz; [D₈]thf; 25 °C): δ 2.12 [br. s, 4H, HB for

1,2-Bis{[chloro(1,1-dimethylethyl)phosphino]thio}-1,2-

δ(¹¹B) = −7.0, −8.0, −9.1 ppm], 2.43 [br. s, 2H, HB for δ(¹¹B) = dicarba-closo-dodecaborane(12) (26). A solution of 4 (60 mg,

−9.1 ppm], 2.46 [br. s, 3H, HB for δ(¹¹B) = −5.0, −11.3 ppm], 0.23 mmol) in CD₂Cl₂(0.4 mL) was cooled to −30 °C and a

2.90 [br. s, 1H, HB for δ(¹¹B) = 0.5 ppm], 7.43 (m, 3H, Ph), 7.66 solution of t-BuPCl₂(80 mg, 0.50 mmol) in CD₂Cl₂(0.2 mL)

(m, 2H, Ph). ¹¹B{¹H} NMR (160.5 MHz; [D₈]thf; 25 °C): δ −11.3 was added. The progress of the reaction was monitored by ³¹P

(2B), −9.1 (3B), −8.0 (1B), −7.0 (2B), −5.0 (1B), 0.5 (1B). ¹¹B and ²⁹Si NMR spectroscopy. After 1 d at r.t., the mixture con-

1

NMR (160.5 MHz; [D₈]thf; 25 °C): δ −11.3 [d, J(¹¹B,¹H) = 167 tained 5 (5%), B₁₀H₁₀C₂[SPCl(t-Bu)]₂26 (45%) and unidentified

Hz, 2B], −9.1 [d, ¹J(¹¹B,¹H) = 173 Hz, 3B], −8.0 (d, 1B), −7.0 [d, intermediate products (50%) together with Me₂SiCl₂and

1

¹J(¹¹B,¹H) = 153 Hz, 2B], −5.0 [d, J(¹¹B,¹H) = 154 Hz, 1B], 0.5 t-BuPCl₂.

[d, ¹J(¹¹B,¹H) = 185 Hz, 1B]. EI-MS (70 eV) for C₈H₁₅B₁₀PS₂

26: ¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 1.29 [m, 9H,

3

(314.4): m/z = 314 ([M⁺], 100%), 280 (10), 266 (4), 249 (5), 237 CH₃, J(³¹P,¹H) = 15.0 Hz], 1.30 [m, 9H, CH₃, J(³¹P,¹H) = 15.0

([M⁺− C₆H₅], 15), 222 (5), 205 (3), 191 (4). Hz]. ¹³C{¹H} NMR (125.8 MHz; CD₂Cl₂; 25 °C): δ 26.34 [d, CH₃,

2,7-Diphenyl-4,5,9,10-bis[1,2-dicarba-closo-dodecaborano- ²J(³¹P,¹³C) = 18.3 Hz], 26.35 [d, CH₃, ²J(³¹P,¹³C) = 18.3 Hz],

(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane (25). A solu- 38.86 [d, CP, J(³¹P,¹³C) = 34.6 Hz], 38.87 [d, CP, J(³¹P,¹³C) =

tion of 4 (125 mg, 0.47 mmol) in CD₂Cl₂(0.6 mL) was cooled 34.6 Hz], 86.3 [d, C(carb), ²J(³¹P,¹³C) = 23.8 Hz, ¹Δ^10/11B[¹³C

to −30 °C and PhPCl₂(0.063 mL, 0.47 mmol) was added (carb)] = −9.5 ppb], 86.5 [d, C(carb), ²J(³¹P,¹³C) = 23.8 Hz,

through a microsyringe. The progress of the reaction was ¹Δ^10/11B[¹³C(carb)] = −9.5 ppb]. ³¹P{¹H} NMR (202.5 MHz;

monitored by ³¹P and ²⁹Si NMR spectroscopy. After 30 min at CD₂Cl₂; 25 °C): δ 174.0.

1

r.t., the mixture contained 21 (90%) and 25 (5%) together with

Me₂SiCl₂and side products B₁₀H₁₀C₂[SPCl(Ph)]₂(ca. 5%). Vola-

Reaction of 4 with Cl₂PCH₂PCl₂

tile materials were removed in a vacuum to give the mixture

2-Dichlorophosphinomethyl-4,5-[1,2-dicarba-closo-dodeca-

containing 21 (90%), 25 (5%), B₁₀H₁₀C₂[SPCl(Ph)]₂(5%) and borano(12)]-1,3,2-dithiaphospholane (27), 2-{4,5-[1,2-dicarba-

unidentified intermediate products. The residue was dissolved closo-dodecaborano(12)]-1,3,2-dithiaphospholan-2-yl}methyl-

in [D₈]thf; after 30 min at r.t., the solution contained 21 4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphospho-

(>95%). Volatile materials were removed in a vacuum, the lane (28) and 2,4,9,11-tetrachloro-6,7,13,14-bis[1,2-dicarba-

residue was dissolved in CD₂Cl₂. Transparent colourless crys- closo-dodecaborano(12)]-2,4,9,11-tetraphospha-1,5,8,12-tetra-

tals of 25 were grown from CD₂Cl₂solution after 2 weeks at thiacyclotetradecane (29). A solution of 4 (53 mg, 0.20 mmol)

−30 °C; m.p. 145–150 °C. The principle structure was con- in [D₈]toluene (0.6 mL) was cooled to 0 °C and Cl₂PCH₂PCl₂

firmed by X-ray analysis, although severe disorder in the (0.034 mL, 0.25 mmol) was added through a microsyringe. The

region of one of the phenyl groups prevented an exact determi- progress of the reaction was monitored by ³¹P and ²⁹Si NMR

nation of a meaningful data set.

spectroscopy. After 15 min at r.t., the mixture contained 27

25: H{¹¹B} NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 2.19 [br. s, (80%), 28 (15%), 29 (<5%) and several unidentified intermedi-

2H, HB for δ(¹¹B) = −9.2 ppm], 2.27 [br. s, 4H, HB for δ(¹¹B) = ates together with Me₂SiCl₂and Cl₂PCH₂PCl₂(Fig. 5). Trans-

−9.2 ppm], 2.42 [br. s, 4H, HB for δ(¹¹B) = −2.8 ppm], 2.57 [br. parent colourless crystals of 29 for X-ray analysis were grown

s, 4H, HB for δ(¹¹B) = −9.2 ppm], 2.62 [br. s, 4H, HB for δ(¹¹B) = from [D₈]toluene solution after 1 week at r.t.; m.p. 58–62 °C.

−6.9 ppm], 3.39 [br. s, 2H, HB for δ(¹¹B) = −9.2 ppm], 7.50 The product 29 is hardly soluble in [D₈]toluene and decom-

(m, 6H, Ph), 7.75 (m, 4H, Ph). ¹¹B{¹H} NMR (160.5 MHz; poses in CD₂Cl₂to 27, 28 and 1,1-bis(dichlorophosphino)

CD₂Cl₂; 25 °C): δ −9.2 (12B), −6.9 (4B), −2.8 (4B). EI-MS (70 methane.

1

eV) for C₁₆H₃₀B₂₀P₂S₄(628.8): m/z = 314 ([M/2⁺], 100), 280 (8),

27: ¹H NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.13 [dd,

266 (4), 249 (5), 237 ([M/2⁺− C₆H₅], 15), 222 (5), 205 (3), 2H, CH₂, ²J(³¹P_PCl,¹H) = 20.4 Hz, ²J(³¹P_PS,¹H) = 8.2 Hz].

191 (4).

¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 3.47 [dd, 2H, CH₂,

2-(1,1-Dimethylethyl)-4,5-[1,2-dicarba-closo-dodecaborano- ²J(³¹P_PCl,¹H) = 19.7 Hz, ²J(³¹P_PS,¹H) = 9.2 Hz].

(12)]-1,3,2-dithiaphospholane (5) and 2,7-bis(1,1-dimethyl-

29: EI-MS (70 eV) for C₆H₂₄B₂₀P₄S₄Cl₄(706.4): m/z = 489

ethyl)-4,5,9,10-bis[1,2-dicarba-closo-dodecaborano(12)]-2,7- ([M⁺− P₂CH₂Cl₄], 20%), 443 (2), 353 ([M/2⁺], 15), 318 ([M/2⁺−

diphospha-1,3,6,8-tetrathiacyclodecane (6). A solution of 4 Cl], 5), 251 ([M/2⁺− PCl₂], 30), 237 ([M/2⁺− CH₂PCl₂], 100).

(84 mg, 0.32 mmol) in CD₂Cl₂(0.4 mL) was cooled to 0 °C and

2,7-Bis{(4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

added to t-BuPCl₂(50 mg, 0.32 mmol). The progress of the dithiaphospholan-2-yl)methyl}-4,5,9,10-bis[1,2-dicarba-closo-

reaction was monitored by ³¹P and ²⁹Si NMR spectroscopy. dodecaborano(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane

After 2 h at r.t., the mixture contained 5 (55%), 6 (5%), side (30), and (28).. A solution of 4 (72 mg, 0.27 mmol) in [D₈]-

products B₁₀H₁₀C₂[SPCl(t-Bu)]₂26 (10%), unidentified toluene (0.6 mL) was cooled to −30 °C and Cl₂PCH₂PCl₂

5040 | Dalton Trans., 2014, 43, 5021–5043

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1

(0.018 mL, 0.13 mmol) was added through a microsyringe. The

32: H NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 1.47 [t, 4H,

progress of the reaction was monitored by ³¹P and ²⁹Si NMR CH₂, ²J(³¹P,¹H) + ³J(³¹P,¹H) = 21.4 Hz].

spectroscopy. After 1 h at r.t., the mixture contained 28 (65%),

2,7-Bis{2-(4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-

30 (30%) and unidentified side products together with dithiaphospholan-2-yl)ethyl}-4,5,9,10-bis[1,2-dicarba-closo-

Me₂SiCl₂. Volatile materials were removed in a vacuum (1 h, dodecaborano(12)]-2,7-diphospha-1,3,6,8-tetrathiacyclodecane

8 × 10⁻³Torr), the residue was dissolved in CD₂Cl₂to give a (33), (32) and dimer (34). A solution of 4 (88 mg, 0.33 mmol)

mixture containing 28 (45%) and 30 (65%).

in [D₈]toluene (0.6 mL) was cooled to −30 °C and Cl₂PCH₂PCl₂

1

28: H NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.26 [t, 2H, (0.025 mL, 0.16 mmol) was added through a microsyringe. The

CH₂, ²J(³¹P,¹H) = 14.3 Hz]. ¹H NMR (500.13 MHz; CD₂Cl₂; progress of the reaction was monitored by ³¹P and ²⁹Si NMR

2

25 °C): δ 3.53 [t, 2H, CH₂, J(³¹P,¹H) = 13.5 Hz]. EI-MS (70 eV) spectroscopy. After 1 d at r.t., volatile materials were removed

for C₅H₂₂B₂₀P₂S₄(488.7): m/z = 489 ([M⁺], 85%).

in a vacuum (2 h, 8 × 10⁻³Torr) to give a mixture containing

30: ¹H NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 2.66 [dd, 32 (95%) and 33 (5%). The residue was dissolved in CD₂Cl₂;

4H, CH₂, ²J(³¹P_P(2),¹H) = 16.6 Hz, ²J(³¹P_P(1),¹H) = 9.5 Hz]. after 1 h at r.t. the mixture contained 32 (55%), 33 (35%) and

¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 3.47 [dd, 4H, CH₂, 34 (10%). A white powder was formed showing rather low solu-

²J(³¹P_P(2),¹H) = 19.7 Hz, ²J(³¹P_P(1),¹H) = 9.2 Hz].

bility in CD₂Cl₂. Volatile materials were removed in a vacuum,

the residue was dissolved in [D₈]thf. After 1 h at r.t. the

mixture contained 32 (90%) and 33 (10%).

32: ¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 2.49 [t, 4H,

Reaction of 4 with Cl₂PCH₂CH₂PCl₂

2-(2-Dichlorophosphinoethyl)-4,5-[1,2-dicarba-closo-dodeca- CH₂, ²J(³¹P,¹H) + ³J(³¹P,¹H) = 21.2 Hz]. ¹H{¹¹B} NMR (500.13 MHz;

borano(12)]-1,3,2-dithiaphospholane (31) and 2-{2-(4,5-[1,2- [D₈]thf; 25 °C): δ 2.13 [br. s, 4H, HB for δ(¹¹B) = −9.3 ppm], 2.40

dicarba-closo-dodecaborano(12)]-1,3,2-dithiaphospholan-2-yl)- [br. s, 2H, HB for δ(¹¹B) = −9.3 ppm], 2.43 [br. s, 2H, HB for

ethyl}-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-dithia- δ(¹¹B) = −6.9 ppm], 2.47 [br. s, 4H, HB for δ(¹¹B) = −12.7 ppm],

phospholane (32). A solution of 4 (45 mg, 0.17 mmol) in [D₈]- 2.54 [t, 4H, CH₂, ²J(³¹P,¹H) + ³J(³¹P,¹H) = 19.0 Hz], 2.56 [br. s, 4H,

toluene (0.6 mL) was cooled to 0 °C and Cl₂PCH₂CH₂PCl₂HB for δ(¹¹B) = −11.1 ppm], 2.80 [br. s, 2H, HB for δ(¹¹B) =

(0.030 mL, 0.20 mmol) was added through a microsyringe. The −1.4 ppm], 2.91 [br. s, 2H, HB for δ(¹¹B) = −9.3 ppm]. ¹¹B{¹H}

progress of the reaction was monitored by ³¹P and ²⁹Si NMR NMR (160.5 MHz; [D₈]thf; 25 °C): δ −12.7 (4B), −11.1 (4B), −9.3

spectroscopy. After 1 h at r.t., the mixture contained 31 (50%), (8B), −6.9 (2B), −1.4 (2B). EI-MS (70 eV) for C₆H₂₄B₂₀P₂S₄(502.7):

32 (50%) and several unidentified intermediates together with m/z = 503 ([M⁺], 3), 327 (3), 265 ([M⁺− C₂H₁₀B₁₀S₂P], 20), 237

Me₂SiCl₂and Cl₂PCH₂CH₂PCl₂.

([C₂H₁₀B₁₀S₂P], 100), 207 ([C₂H₁₀B₁₀S₂H], 30).

33: ¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 2.35 [m, 4H,

P(2)CH₂], 2.65 [m, 4H, P(1)CH₂].

31: ¹H NMR (500.13 MHz; [D₈]toluene; 25 °C): δ 1.37 (m,

2H, S₂PCH₂), 1.89 (m, 2H, Cl₂PCH₂).

Table 6 Crystallographic data of the ortho-carborane derivatives 6, 7(S), and 29

6^a

7(S)

29

Formula

Crystal

C

₁₂H₃₈B₂₀P₂S₄·2CD₂Cl₂

C₆H₁₉B₁₀PS₃

Colourless prism

0.17 × 0.14 × 0.12

133(2)

Orthorhombic

Pbca

C₆H₂₄B₂₀Cl₄P₄S₄·2toluene

Colourless prism

0.18 × 0.14 × 0.12

133(2)

Orthorhombic

Pbca

Colourless prism

0.24 × 0.18 × 0.16

133(2)

Monoclinic

C2/c

Dimensions [mm³]

Temperature [K]

Crystal system

Space group

Lattice parameters

a [pm]

2019.4(4)

1141.0(2)

3185.2(6)

1323.7(3)

1395.0(3)

1814.7(4)

1580.2(3)

1321.9(3)

2026.5(4)

b [pm]

c [pm]

α [°])

β [°]

91.73(3)

γ [°])

Z

8

4

Absorption coeﬃcient μ, [mm⁻¹

Diﬀractometer

Measuring range (ϑ) [°]

Reflections collected

]

0.652

0.514

0.649

STOE IPDS II, MoK_α, λ = 71.073 pm, graphite monochromator

2.02–25.67

16 330

2.24–25.64

15 337

2.01–25.71

22 786

Independent reflections [I ≥ 2σ(I)]

Absorption correction

3048

2204

3059

None^b

Refined parameters

344

0.252/0.090

1.363/−0.519

181

0.127/0.071

0.563/−0.463

243

0.120/0.062

0.694/−0.302

wR₂/R₁[I ≥ 2σ(I)]

Max./min. residual electron density, [e pm⁻³10⁻⁶

]

^aThe unit cell contains 16 methylene chloride molecules which have been treated as a diﬀuse contribution to the overall scattering without

specific atom positions by SQUEEZE/PLATON. ^bAbsorption corrections did not improve the parameter set.

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34: ¹H NMR (500.13 MHz; CD₂Cl₂; 25 °C): δ 2.56 [t, 8H,

J. Organomet. Chem., 2007, 692, 4545–4550; (f) X.-F. Hou,

S. Liu, H. Wang, Y.-Q. Chen and G.-X. Jin, Dalton Trans.,

2006, 5231–5239; (g) S. Cai, J.-Q. Wang and G.-X. Jin,

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L.-H. Weng, Chin. Sci. Bull., 2003, 48, 1733–1736.

CH₂, ²J(³¹P,¹H) + ³J(³¹P,¹H) = 21.8 Hz].

Crystal structure determination of 6, 7(S) and 29

Structure solutions and refinements were carried out with the

program package SHELXTL-PLUS V.5.1.⁴²Details pertinent to

the crystal structure determination are listed in Table 6. Crys-

tals of appropriate size were sealed under argon in Lindemann

capillaries, and the data collections were carried out at 133 K.

CCDC 961682 (6, at 133 K), 961683 [7(S), at 133 K], 961684 (29,

at 133 K) contain the supplementary crystallographic data for

this paper.

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Acknowledgements

Support of this work by the Deutsche Forschungsgemeinschaft is

gratefully acknowledged.

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Article Doi

1,3,2-Dithiaphospholanes with an annelated 1,2-dicarba-closo- dodecaborane(12) unit: Formation and reactivity

DOI: 10.1039/c3dt52753k

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Full text of DOI:10.1039/c3dt52753k

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