The reaction of phenylchlorophosphino-substituted 1,2-dicarba-closo-dodecaboranes(12) with elemental sulfur and molecular structures of rac-1,2-bis(phenylchlorophosphino)-1,2-dicarba-closo-dodecaborane(12) and 1-phenylchlorothiophosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12)

Article abstract of DOI:10.1016/S0277-5387(98)00330-1

rac-1,2-Bis(phenylchlorophosphino)-1,2-dicarba-closo-dodecaborane(12) (1) reacts with four equivalents of sulfur at 185-190°C in undecane to give the cyclic anhydride of 1,2-bis(phenylthiophosphoryl)-1,2-dicarba-closo-dodecaboranyl(12)- dithiodiphosphinic acid (2). Under comparable conditions, 1-phenyl-chlorophosphino-1,2-dicarba-closo-dodecaborane(12) (4) and 1-phenyl-chlorophosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12) (5) react with sulfur to give 1-phenylchlorothiophosphino-1,2-dicarba-closo-dodecaborane(12) (6) and 1-phenylchlorothiophosphino-2-phenyl-1,2-dicarba-closo-dodecaborane(12) (7). Compounds 4-7 were characterized by ¹H, ³¹P, ¹³C and ¹¹B NMR spectroscopy and elemental analysis, and X-ray structure determinations were carried out on 1 and 7.

Full text of DOI:10.1016/S0277-5387(98)00330-1

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Polyhedron 07 "0888# 434Ð441
PERGAMON
The reaction of phenylchlorophosphino!substituted 0\1!dicarba!
closo!dodecaboranes"01# with elemental sulfur and molecular
structures of rac!0\1!bis"phenylchlorophosphino#!0\1!dicarba!
closo!dodecaborane"01# and 0!phenylchlorothiophosphino!
1!phenyl!0\1!dicarba!closo!dodecaborane"01#
Viktor P[ Balema\ Ste}en Blaurock\ Evamarie Hey!Hawkinsꢀ
Institut fur Anorganische Chemie der Universitat Leipzig\ Talstrasse 24\ D!93092 Leipzig\ Germany
Ã
Ã
Received 09 June 0887^ accepted 10 July 0887
Abstract
rac!0\1!Bis"phenylchlorophosphino#!0\1!dicarba!closo!dodecaborane"01# "0# reacts with four equivalents of sulfur at 074Ð089>C
in undecane to give the cyclic anhydride of 0\1!bis"phenylthiophosphoryl#!0\1!dicarba!closo!dodecaboranyl"01#!dithiodiphosphinic
acid "1#[ Under comparable conditions\ 0!phenyl!chlorophosphino!0\1!dicarba!closo!dodecaborane"01# "3# and 0!phenyl!
chlorophosphino!1!phenyl!0\1!dicarba!closo!dodecaborane"01# "4# react with sulfur to give 0!phenylchlorothiophosphino!0\1!
dicarba!closo!dodecaborane"01# "5# and 0!phenylchlorothiophosphino!1!phenyl!0\1!dicarba!closo!dodecaborane"01# "6#[ Com!
pounds 3Ð6 were characterized by 0H\ 20P\ 02C and 00B NMR spectroscopy and elemental analysis\ and X!ray structure determinations
were carried out on 0 and 6[ Þ 0888 Elsevier Science Ltd[ All rights reserved[
Keywords] Carbaboranylchlorophosphines^ Carbaboranylchlorothiophosphines
0[ Introduction
0\1!dicarba!closo!dodecaborane"01# "3# and 0!phenylchl
orophosphino!1!phenyl!0\1!dicarba!closo!dodecabor!
ane"01# "4# with sulfur[ Although 0 has been known for
more than 29 years ð3Ł\ its reaction with chalcogens has
not yet been reported[ While the reaction of 3 and 4
with sulfur forms carbaboranyl!chlorothiophosphines\ 0
unexpectedly gives the cyclic anhydride of 0\1!bis"phen!
ylthiophos!phoryl#!0\1!dicarba!closo!dodecaboranyl"01#!
dithio!diphosphinic acid "1#[
The oxidation of organic derivatives of trivalent phos!
phorus by sulfur is probably the most widely investigated
reaction in the chemistry of organophosphorus com!
pounds after the Arbuzov reaction ð0Ł[ The sulfurization
of compounds containing P"III#Ðhalogen bonds has been
extensively studied because of its importance for the syn!
thesis of a wide range of organic derivatives of phos!
phorus ð1\ 2Ł[ The reactions which have been reported in
the literature proceed with retention of the PÐX bond
"Xꢁhalide# to give the corresponding thiophosphorus
acids "eqn "0##[
1[ Results and discussion
0\1 ! Bis"phenylchlorophosphino# ! 0\1 ! dicarba !closo!
dodecaborane"01# is obtained as a mixture of dia!
stereomers "rac and meso# ð3Ł\ from which one isomer can
be isolated by fractional crystallization from hexane:
toluene[ This was shown to be the rac isomer by X!ray
structure analysis "vide infra#[
"0#
Here we report on our studies of the reactions
of
rac!0\1!bis"phenylchlorophosphino#!0\1!dicarba!
rac!0\1!Bis"phenylchlorophosphino#!0\1!dicarba!
closo!dodecaborane"01# "0# reacts with two equivalents
of sulfur in undecane over 5 h at 074Ð089>C to give an
inseparable mixture of products[ The 20P NMR spectrum
of the reaction mixture exhibits several signals at 79[0 "d\
closo!dodecaborane"01# "0#\ 0!phenylchlorophos!phino!
ꢀ Corresponding author[
9166!4276:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[
PII] S9166!4276"87#99229!0

435
V[P[ Balema et al[ : Polyhedron 07 "0888# 434Ð441
JPP 09 Hz#\ 68[8 "d\ JPP 09 Hz#\ 61[3 "d\ JPP 09 Hz#\ 69[6
"d\ JPP 09 Hz# and 64[1 ppm "s#[ However\ when four
equivalents of sulfur are employed\ one major product is
formed "64[1 ppm\ s# and can be isolated in 46) yield[
Its spectroscopic data "20P\ 0H\ 00B and 02C NMR#\ melt!
ing point and elemental analyses are in agreement with
the cyclic anhydride of 0\1!bis"phenylthiophos!phoryl#!
0\1!dicarba!closo!dodecaboranyl"01#!dithio!
diphosphinic acid "1#\ which was also obtained from 0\1!
bis"phenylphosphino#!0\1!dicarba!closo!dodeca!bor!
ane"01# and sulfur ð4Ł[ The four doublets which are
observed for the reaction mixture indicate the initial for!
mation of rac! and meso!0!"phenylchlorothio!
phosphino#!1!phenylchlorophosphino!0\1!dicarba!
closo!dodecaborane"01# "2# "eqn "1## "see NMR data#[
"2#
The fact that di}erent sulfurization products are
obtained on reacting 0 or 3 and 4 with sulfur under com!
parable reaction conditions is not readily explained[ The
possibility that 1 is formed from 0 and H1S\ a possible
"1#
To understand the course of the reaction between 0
and sulfur\ we also studied the reaction of 0!phenyl!
chlorophosphino!0\1!dicarba!closo!dodecaborane
"01# "3# and 0!phenyl!1!phenylchlorophosphino!0\1!
dicarba!closo!dodecaborane"01# "4#\ both of which were
prepared from Li derivatives of the corresponding o!
carbaboranes and PhPCl10[ Compounds 3 and 4 react
with sulfur over 5 h at 074Ð089>C in undecane to give the
carbaboranylphenyl!chlorothiophosphines 5 and 6ꢀ ð5Ł
"eqn "2##\ which were characterized by NMR spec!
troscopy and elemental analysis[ Additionally\ an X!ray
structure determination was carried out on 6[ The same
products were obtained with an excess of sulfur "two
equivalents#[
pyrolysis product of undecane in the presence of sulfur ð6Ł\
can be excluded as the products that would be expected
here are not obtained in the reactions of 3 and 4 with
sulfur[ Apparently\ the electron!withdrawing properties of
the 0\1!dicarba!closo!dodecaboranyl"01# fragment ð7Ð09Ł
and the presence of a second phosphine group determine
the reactivity of carbaboranylphosphines[ The most likely
_rst step in the reaction of 0 with sulfur\ which is also
supported by NMR studies\ is the oxidation of one phos!
phine group to give 2 "eqn "1##\ while the further steps in
the formation of 1 are unclear[ Abstraction of Cl atoms
from 2 by sulfur and an addition of further sulfur atoms
to intermediate compounds seems likely but could not be
proved spectroscopically[ The assistance of the second
PhPCl group in 0 seems to be crucial for the abstraction
of chlorine\ similar to the abstraction of halogen from
hydrocarbon halides ð6Ł\ since for 3 and 4 the reaction
stops at the stage of the carbaboranylphenyl!
chlorothiophosphines 5 and 6[ Similarly\ 0\1!bis"phenyl!
phosphino#!0\1!dicarba!closododecaborane"01# reacts with
sulfur to give a carbaboranylphenylthiophosphine inter!
mediate\ which yields 1 as the _nal product ð4Ł[
0 Although the synthesis of 4 was reported earlier ð5Ł\ no spectroscopic
data were given and the published melting point is 19>C lower than that
determined by us for 4[ Similarly\ di}erences between our results and
those reported previously ð5Ł were also observed for 0!phe!
nylchlorothiophos!phine!1!phenyl!0\1!dicarba!closo!
dodecaborane"01# "6#[

V[P[ Balema et al[ : Polyhedron 07 "0888# 434Ð441
436
1[0[ NMR spectra
carbon atoms of 0\ 1\ 4 and 6 are observed in the range
71Ð75 ppm\ while 3 and 5 exhibit these signals at 63Ð
65 ppm[ This phenomenon of low!_eld shift of 20P NMR
signals together with high!_eld shift of the 02C NMR
signals of the cluster carbon atoms in the spectra of 0!
substituted o!carbaboranyl"01#!phosphorus compounds
compared with 0\1!disubstituted o!carbaboranyl"01#!
phosphorus compounds is apparently a general trend for
phosphorus derivatives of o!carbaborane"01# "cf[ð4Ł#[ As
expected\ the 0JCP coupling constant of the thiophosphine
derivatives 5 and 6 "40 and 33 Hz# is smaller than that of
the corresponding phosphine derivatives 3 and 4 "86 and
83 Hz#[
0
Table 0 lists H\ 20P\ 02C and 00B NMR spectroscopic
data for 0\ 1 and 3Ð6\ as well as 20P NMR data of 2[ The
NMR spectra of 1 have been discussed earlier ð4\09Ł[
Compounds 0 and 3Ð6 exhibit singlets in their 20P NMR
spectra at 79[8\ 80[2\ 70[0\ 68[4 and 60[4 ppm\ respec!
tively[ For the rac and meso isomers of the intermediate
2\ doublets are observed at 79[0\ 68[8\ 61[3 and 69[6 with
JPP 09 Hz[ The _rst two signals can be assigned to the
PhPCl group\ and the latter to the PhP"S#Cl group by
comparison with 0 and 3Ð6[ While similar chemical shifts
are observed in the 20P NMR spectra of 0 and 4\ the
corresponding signal of 3 is shifted to low _eld by about
09 ppm[ The signals for the thiophosphine groups of 2\ 5
and 6 are shifted to high _eld by ca[ 09Ð01 ppm compared
with the corresponding phosphine groups in 0\ 3 and 4[
In the 02C NMR spectra\ the signals of the cluster
In the 00B NMR spectra\ the signals of compounds 0\
1 and 3Ð6 are observed in the expected range of −0 to
03 ppm with coupling constants JBH of 025Ð072 Hz[ In
the 0H NMR spectrum\ the signals of the Ph groups are
observed between 6[5 and 5[5 ppm and overlap partially[
Table 0
NMR data for compounds 0Ð6
Compound
20P "ppm#:
00B "ppm#:JBH "Hz#
0H "ppm#
02C "ppm#:JCP or JCH "Hz#
JPP "Hz#
0 "rac#
79[8
9[9:036 "1B#\
−5[5:042 "1B#\
−09[1:033 "3B#\
−00[8:034 "1B#
6[44 "m\ 1H\ Ph#\ 5[85 "m\ 2H\ Ph#\
2[4Ð0[8 "m\ v br\ 09H\ BÐH#
023[2\ 022[3\ 022[1\ 018[6
"Ph#^ 74[9 "m\ CclusterÐP#
1 ð4Ł "rac#
64[1
−1[6:056 "1B#\ −3[2:055 7[07 "m\ 1H\ Ph#\ 5[80 "m\ 2H\ Ph#\
025[2\ 022[3\ 029[1\ 017[5
"Ph#^ 74[7 "m\ CclusterÐP#
"1B#\
2[4Ð0[8 "m\v br\ 09H\ BÐH#
−09[2 "5B#
2
79[0 "d#:09\
68[8 "d#:09\
61[3 "d#:09\
69[6 "d#:09
3
4
5
80[2
70[0
68[4
−0[2:025 "0B#\ −0[8:039 6[29 "m\ 1H\ Ph#\ 5[86 "m\ 0H\ Ph#\
022[3\ 021[4:29\ 018[6\
"0B#\ −6[2:041 "1B#\
−00[1:058 "1B#\
−01[4:060 "1B#\ −02[8:072
"1B#\
5[81 "m\ 1H\ Ph#\ 2[18 "s\ v br\ 0H\ CÐ 018[5 "Ph#^ 63[5:86 "Ccluster
Hcluster#\ 2[0Ð0[7 "m\ v br\ 09H\ BÐH#
Ð
#
P#\ 52[3:083 "0JCH#:09 "2JCP
"CclusterÐH#
−9[5:037 "0B#\ −2[3:042 6[34 "m\ 1H\ Ph#\ 6[29 "m\ 1H\ Ph#\
023[4:22\ 022[0:7\ 021[7\
"0B#\ −6[8:059 "1B#\
−8[1:045 "3B#\
−00[7 "0B#\
5[86 "m\ 1H\ Ph#\ 5[89 "m\ 3H\ Ph#\ 2[3Ð 021[3\ 020[6\ 020[5 "Ph#^
0[7 "m\ v br\ 09H\ BÐH#
76[2:06 "2JCP# "CclusterÐPh#\
74[9:83 "0JCP# "CclusterÐP#
−01[8 "0B#\
−0[0:038 "0B#\ −2[4:049 6[56 "m\ 1H\ Ph#\ 5[85 "m\ 0H\ Ph#\
"0B#\ −5[6:027 "0B#\
023[7\ 022[4\ 021[5\ 029[7
5[75 "m\ 1H\ Ph#\ 3[22 "s\ 0H\ CÐHcluster#\ "Ph#^ 64[3:40 "0JCP
#
−6[6:030 "0B#\
−00[5 "1B#\
−01[8 "1B#\
−02[7 "1B#
2[4Ð0[7 "m\ v br\ 09H\ BÐH#
"CclusterÐP#\ 54[3
6
60[4
9[7:049 "0B#\
6[33 "m\ 1H\ Ph#\ 6[11 "m\ 1H\ Ph#\
023[0:3\ 022[8:01\ 022[9\
−0[8:044 "0B#\
−6[5:063 "1B#\ −09[9:036 0[8 "m\ v br\ 09H\ BÐH#
"5H#
5[89 "m\ 1H\ Ph#\ 5[63 "m\ 3H\ Ph#\ 2[3Ð 021[2\ 020[5\ 029[4 "Ph#\ 76[1
"CclusterÐPh#\ 71[4:33 "0JCP
"CclusterÐP#
#

437
V[P[ Balema et al[ : Polyhedron 07 "0888# 434Ð441
1[1[ X!ray structure analyses of rac!0\1!bis"phenylchloro!
phosphino#!0\1!dicarba!closo!dodecaborane"01# "0# and
0!phenylchlorothiophosphino!1!phenyl!0\1!di!carba!closo!
dodecaborane"01# "6#
the range 249Ð3999 cm−0[ Melting points were deter!
mined in capillaries and are uncorrected[ PhPCl1 is com!
mercially available "Aldrich#[
2[0[ Synthesis of rac!0\1!bis"phenylchlorophosphino#!0\1!
dicarba!closo!dodecaborane"01# "0#
Crystals of 0 were obtained from hexane:toluene and
crystals of 6 from hexane at room temperature[ In both
compounds\ the P atoms are chiral centers[ 0 crystallizes
0 was prepared according to the literature procedure
ð3Ł from 4[9 g "23[6 mmol# 0\1!dicarba!closo!dode!
caborane"01# and 01[4 g "58[3 mmol# PhPCl1 in ether[ The
diastereomers were separated by recrystallization of the
reaction product from a hexane:toluene mixture at room
temperature[ Yield of rac!0\1!bis"phenylchlorophos!
phino#!0\1!dicarba!closo!dodecaborane"01# "0# 6[1 g
"45)#[ m[p[ 048Ð050>C[ IR "cm−0#] 2964\ 2948\ 2994
"nCH#^ 1514\ 1598\ 1485\ 1467\ 1440 "nBH#^ 0848\ 0773\
0795\ 0646 "nPh#^ 0473\ 0461\ 0370\ 0324\ 0272\ 0224\
0294\ 0164\ 0074\ 0059\ 0989\ 0958\ 0914\ 888\ 869\ 823\
891\ 765\ 727\ 687\ 632\ 613\ 588\ 578\ 563\ 511\ 450\ 496\
374\ 310[
¹
in the centrosymmetric space group P0 "No[ 1#[ Due to
the crystallographic center of inversion\ both enanti!
omers "R\R# and "S\S# are present in the unit cell "Fig[
0#[ 6 crystallizes in the orthorhombic space group Pbca
"No[ 50# with eight formula units in the unit cell[ Due to
the crystallographic center of inversion\ both enanti!
omers "R# and "S# are present in the unit cell "Fig[ 1#[
The bond lengths and angles of the C1B09H09 fragment
"Table 1 and Table 2# show no remarkable deviations
from comparable structures ð4\00Ð04Ł[ The PÐCl bond
lengths in 0 and 6 ð0] P"0#ÐCl"0# 1[940"0#\ P"1#ÐCl"1#
Ä
Ä
Ä
1[947"0# A^ 6] P"0#ÐCl"0# 1[9093"7# AŁ and the PÐS bond
length in 6 ðP"0#ÐS"0# 0[8196"7# AŁ lie in the range
observed for PÐCl bonds in P"O#Cl ð0[880"1# and
1[93"3# AŁ ð05Ł or P"S#Cl groups ð1[960Ð1[92"0# AŁ ð06\
2[1[ Synthesis of 0!phenylchlorophosphino!0\1!dicarba!
closo!dodecaborane"01# "3#
Ä
Ä
07Ł and P1S bonds in comparable compounds ð1] P1S
Ä
0[8043"8#\ 0[8107"8# AŁ ð4Ł[
At 7>C\ a suspension of 0!lithio!0\1!dicarba!closo!
dodecaborane"01# in benzene\ obtained from 2[9 g
"19[7 mmol# of 0\1!dicarba!closo!dodecaborane"01# and
2[ Experimental
BuLi "10 mmol\ 0[5 M in hexane# in benzene "14 cm−2
#
All experiments were carried out under puri_ed dry
argon[ Solvents were dried and freshly distilled under
argon[ NMR spectra] Avance DRX 399 "Bruker#\ stan!
dards] 0H NMR "399 MHz#] traces of protonated solvent\
C5D5\ 02C NMR "099[5 MHz#] internal solvent\ 20P NMR
"051 MHz#] external 74) H2PO3\ 00B NMR] external
BF2 = Et1O[ The IR spectra were recorded as KBr mulls
on a PerkinÐElmer System 1999 FTÐIR spectrometer in
was added to a solution of 4[8 g "22[2 mmol# PhPCl1 in
benzene "14 cm−2#[ The reaction mixture was kept at
room temperature for 01 h\ then the solvent was removed
and the remaining solid was dissolved in pentane and
_ltered[ Recrystallization from pentane gave 2[5 g "59)#
of 3 "at room temperature#[ m[p[ 47Ð50>C[ IR "cm−0#]
2945 "nCH#\ 1483 "nBH#\ 0478\ 0371\ 0325\ 0296\ 0150\
0110\ 0064\ 0006\ 0989\ 0969\ 0911\ 888\ 850\ 767\ 738\
Fig[ 0[ Molecular structure of 0[ Only one of the enantiomers with its atom numbering scheme is shown "ORTEP\ 49) probability\ SHELXTL
PLUS^ XP# ð08Ł[ Hydrogen atoms omitted for clarity[

V[P[ Balema et al[ : Polyhedron 07 "0888# 434Ð441
438
Fig[ 1[ Molecular structure of 6[ Only one of the enantiomers with its atom numbering scheme is shown "ORTEP\ 49) probability\ SHELXTL
PLUS^ XP# ð08Ł[ Hydrogen atoms omitted for clarity[
Table 1
Ä
Selected bond lengths "A# and angles "># for 0
P"0#ÐC"00#
P"0#ÐCl"0#
P"1#ÐC"1#
B"0#ÐC"1#
B"1#ÐC"0#
B"3#ÐC"1#
B"4#ÐC"1#
C"0#ÐC"1#
C"00#ÐC"05#
C"02#ÐC"03#
C"04#ÐC"05#
C"10#ÐC"15#
C"12#ÐC"13#
C"14#ÐC"15#
0[710"1#
1[940"0#
0[775"1#
0[615"2#
0[604"2#
0[629"2#
0[600"2#
0[691"2#
0[284"2#
0[263"4#
0[268"3#
0[285"3#
0[274"5#
0[269"3#
P"0#ÐC"0#
0[768"1#
0[704"2#
1[947"0#
0[617"2#
0[695"2#
0[621"2#
0[698"2#
0[274"2#
0[282"3#
0[269"4#
0[284"3#
0[277"4#
0[261"5#
P"1#ÐC"10#
P"1#ÐCl"1#
B"0#ÐC"0#
B"2#ÐC"0#
B"3#ÐC"0#
B"5#ÐC"1#
C"00#ÐC"01#
C"01#ÐC"02#
C"03#ÐC"04#
C"10#ÐC"11#
C"11#ÐC"12#
C"13#ÐC"14#
C"00#ÐP"0#ÐC"0#
C"0#ÐP"0#ÐCl"0#
C"10#ÐP"1#ÐCl"1#
C"1#ÐC"0#ÐP"0#
B"1#ÐC"0#ÐP"0#
B"3#ÐC"0#ÐP"0#
099[37"09#
C"00#ÐP"0#ÐCl"0#
C"10#ÐP"1#ÐC"1#
C"1#ÐP"1#ÐCl"1#
B"2#ÐC"0#ÐP"0#
B"0#ÐC"0#ÐP"0#
C"0#ÐC"1#ÐP"1#
090[42"7#
099[60"6#
090[57"7#
001[78"02#
011[1"1#
019[10"03#
029[9"1#
010[1"1#
008[5"1#
014[1"1#
008[5"2#
019[2"2#
008[2"2#
014[7"1#
008[6"2#
019[4"3#
090[28"09#
090[92"6#
017[8"1#
098[85"03#
001[08"02#
010[5"1#
097[26"02#
004[1"1#
008[8"2#
019[7"2#
008[7"2#
003[7"1#
008[7"2#
019[3"2#
019[1"2#
B"5#ÐC"1#ÐP"1#
B"0#ÐC"1#ÐP"1#
B"4#ÐC"1#ÐP"1#
B"3#ÐC"1#ÐP"1#
C"01#ÐC"00#ÐC"05#
C"05#ÐC"00#ÐP"0#
C"03#ÐC"02#ÐC"01#
C"03#ÐC"04#ÐC"05#
C"11#ÐC"10#ÐC"15#
C"15#ÐC"10#ÐP"1#
C"13#ÐC"12#ÐC"11#
C"15#ÐC"14#ÐC"13#
C"01#ÐC"00#ÐP"0#
C"00#ÐC"01#ÐC"02#
C"04#ÐC"03#ÐC"02#
C"04#ÐC"05#ÐC"00#
C"11#ÐC"10#ÐP"1#
C"12#ÐC"11#ÐC"10#
C"14#ÐC"13#ÐC"12#
C"14#ÐC"15#ÐC"10#

449
V[P[ Balema et al[ : Polyhedron 07 "0888# 434Ð441
Table 2
Selected bond lengths "A# and angles "># for 6
Ä
Cl"0#ÐP"0#
P"0#ÐC"0#
C"0#ÐB"1#
C"0#ÐB"2#
C"0#ÐB"0#
C"1#ÐB"5#
C"1#ÐB"3#
C"8#ÐC"03#
C"8#ÐC"1#
C"02#ÐC"01#
C"01#ÐC"00#
C"3#ÐC"4#
C"5#ÐC"4#
C"6#ÐC"7#
1[9093"7#
0[763"1#
0[692"2#
0[611"2#
0[626"2#
0[605"2#
0[641"2#
0[289"2#
0[494"1#
0[267"2#
0[279"2#
0[280"2#
0[265"3#
0[279"2#
P"0#ÐC"2#
P"0#ÐS"0#
C"0#ÐC"1#
C"0#ÐB"3#
C"1#ÐB"4#
C"1#ÐB"0#
BÐB
C"8#ÐC"09#
C"09#ÐC"00#
C"02#ÐC"03#
C"3#ÐC"2#
C"2#ÐC"7#
C"6#ÐC"5#
0[794"1#
0[8196"7#
0[605"1#
0[629"2#
0[600"2#
0[626"2#
0[654"2#Ð0[689"3#
0[286"2#
0[274"2#
0[280"2#
0[280"2#
0[284"2#
0[264"3#
C"2#ÐP"0#ÐC"0#
C"0#ÐP"0#ÐS"0#
C"0#ÐP"0#ÐCl"0#
B"1#ÐC"0#ÐP"0#
B"3#ÐC"0#ÐP"0#
C"1#ÐC"0#ÐP"0#
C"7#ÐC"2#ÐP"0#
C"09#ÐC"8#ÐC"1#
C"03#ÐC"8#ÐC"09#
C"01#ÐC"00#ÐC"09#
C"8#ÐC"03#ÐC"02#
C"4#ÐC"3#ÐC"2#
C"5#ÐC"6#ÐC"7#
C"5#ÐC"4#ÐC"3#
094[80"7#
C"2#ÐP"0#ÐS"0#
C"2#ÐP"0#ÐCl"0#
S"0#ÐP"0#ÐCl"0#
B"2#ÐC"0#ÐP"0#
B"0#ÐC"0#ÐP"0#
C"3#ÐC"2#ÐP"0#
C"03#ÐC"8#ÐC"1#
C"8#ÐC"1#ÐC"0#
C"00#ÐC"09#ÐC"8#
C"01#ÐC"02#ÐC"03#
C"6#ÐC"5#ÐC"4#
C"3#ÐC"2#ÐC"7#
C"6#ÐC"7#ÐC"2#
002[79"6#
093[61"6#
003[74"3#
019[28"02#
005[20"02#
007[2"1#
011[9"1#
019[57"04#
019[4"1#
019[7"1#
019[2"1#
008[7"1#
008[5"1#
001[16"5#
093[26"5#
006[31"02#
019[62"01#
010[11"01#
010[7"1#
007[8"1#
008[0"1#
019[0"1#
008[6"1#
008[5"1#
019[5"1#
019[0"1#
684\ 634\ 611\ 589\ 517\ 440\ 409\ 375\ 313[ Found] C\
23[24^ H\ 4[37^ Cl\ 01[57[ Calc[] for C7H05B09PCl "175[4#]
C\ 22[40^ H\ 4[47^ Cl\ 01[28)[
2[3[ Reaction of 0\ 3 and 4 with sulfur] general procedure
0 was reacted with four\ and 3 and 4 with one or two
equivalents of sulfur in undecane at 074Ð089>C for 5 h[
Then undecane was removed\ and the remaining solid
dissolved in hexane and _ltered[ Compounds 1\ 5 and 6
were obtained by recrystallization from hexane at room
temperature[
2[2[ Synthesis of 0!phenylchlorophosphino!1!phenyl!0\1!
dicarba!closo!dodecaborane"01# "4#
At 9>C\ a solution of 0!lithio!1!phenyl!0\1!dicarba!
closo!dodecaborane"01#\ obtained from 0[12 g "4[4 mmol#
0!phenyl!0\1!dicarba!closo!dodecaborane"01# and BuLi
"5 mmol\ 0[5 M in hexane# in ether "14 cm−2# was added
to a solution of 9[88 g "4[5 mmol# PhPCl1 in ether
"14 cm−2#[ The reaction was kept at 9>C for 0 h and then
for 01 h at room temperature[ The solvent was removed\
and the remaining solid dissolved in hexane and _ltered[
Recrystallization from hexane at room temperature gave
9[7 g "30)# of 4[ m[p[ 047Ð048>C[ IR "cm−0#] 2328\ 2953\
1814 "nCH#^ 1556\ 1544\ 1591\ 1463\ 1450\ 1435 "nBH#^
0843\ 0776\ 0701 "nPh#^ 0474\ 0382\ 0379\ 0336\ 0324\
0221\ 0295\ 0172\ 0135\ 0121\ 0084\ 0047\ 0095\ 0989\
0961\ 888\ 808\ 775\ 737\ 724\ 792\ 663\ 635\ 578\ 569\
514\ 464\ 404\ 386\ 364\ 321\ 307[ Found] C\ 36[91^ H\
4[70^ Cl\ 8[30[ Calc[] for C03H19B09PCl "251[4#] C\ 35[24^
H\ 4[41^ Cl\ 8[68)[
2[4[ Synthesis of the cyclic anhydride of 0\1!bis"phenyl!
thiophosphoryl#!0\1!dicarba!closo!dodecaboranyl
"01#!dithiodiphosphinic acid "1#
1 was obtained from 0[9 g "1[2 mmol# 0 and 9[2 g
"8[2 mmol# sulfur in undecane "19 cm−2#[ Yield] 9[5 g
"46)#\ m[p[ 115Ð118>C "lit[ 118Ð121>C ð4Ł#[ NMR and IR
spectroscopic data are in agreement with those reported
earlier ð4Ł[
2[5[ Synthesis of 0!phenylchlorothiophosphino!0\1!di!
carba!closo!dodecaborane"01# "5#
5 was obtained from 9[75 g "2[9 mmol# 3 and 9[2 g
"5[1 mmol# sulfur in undecane "19 cm−2#[ Yield] 9[71 g
"75)#\ m[p[ 007Ð008>C[ IR "cm−0#] 2947\ 2930\ 1850\

V[P[ Balema et al[ : Polyhedron 07 "0888# 434Ð441
440
"nCH#^ 1597\ 1479 "nBH#\ 0470\ 0363\ 0326\ 0272\ 0226\
0298\ 0151\ 0078\ 0052\ 0015\ 0986\ 0958\ 0913\ 888\ 826\
806\ 893\ 757\ 744\ 685\ 630\ 572\ 529\ 503\ 480\ 459\ 449\
417\ 375\ 310[ Found] C\ 29[03^ H\ 4[91^ S\ 09[93[ Calc[]
for C7H05B09PSCl "175[4#] C\ 29[54^ H\ 4[13^ S\ 8[78)[
the unit cell parameters[ The studied specimen was a
white single crystal of dimensions 9[3×9[2×9[1 mm[
Crystal data for 6 are as follows] C03H19B09ClPS\
Mꢁ283[77\ space group Pbca "No[ 50#\ orthorhombic\
Ä
Ä
Ä
aꢁ05[558"2# A\
bꢁ7[445"1# A\
cꢁ16[589"5# A\
2
Ä
Vꢁ2838[1"03# A \ at Tꢁ119"1# K\ Zꢁ7\ Dcꢁ0[217 Mg
m−2\ F"999#ꢁ0505\ m"MoKa# ꢁ 9[266 mm−0\ no absorp!
tion correction[
2[6[ Synthesis of 0!phenylchlorothiophosphino!1!phenyl!
0\1!dicarba!closo!dodecaborane"01# "6#
Positions of P\ C\ Cl\ S and B atoms were located by
using direct methods "SHELXTL PLUS# ð08Ł[ Sub!
sequent least!squares re_nement and di}erence electron
density map calculations revealed the positions of the H
atoms[ Final full!matrix least!squares re_nement of 213
parameters with a unit weighting scheme "P\ C\ Cl\ S and
B atoms anisotropic approximation\ H atoms isotropic
approximation# converged to R0ꢁ9[9259\ wR1ꢁ9[9834
ðfor re~ections with I×1s"I#Ł\ R0ꢁ9[9451\ wR1ꢁ9[0079
"all data#[
6 was obtained from 9[43 g "0[4 mmol# 4 and 9[98 g
"2[9 mmol# sulfur in undecane "04 cm−2#[ Yield] 9[3 g
"55)#\ m[p[ 066Ð067>C "lit[ 051Ð052>C ð5Ł#[ IR "cm−0#]
2950\ 1852 "nCH#^ 1563\ 1528\ 1597\ 1482\ 1472\ 1469\
1438 "nBH#\ 0845\ 0787\ 0709 "nPh#^ 0479\ 0383\ 0370\
0360\ 0337\ 0325\ 0239\ 0298\ 0175\ 0151\ 0086\ 0984\
0967\ 0917\ 0993\ 887\ 810\ 894\ 774\ 740\ 790\ 633\ 698\
573\ 513\ 504\ 463\ 419\ 498\ 383\ 372\ 325[ Found] C\
31[27^ H\ 4[90[ Calc[] for C03H19B09PCl "283[4#] C\ 31[47^
H\ 4[96)[
Atomic coordinates\ bond lengths and angles and ther!
mal parameters have been deposited at the Fach!
informationszentrum Karlsruhe\ D!65233 Eggenstein!
Leopoldshafen "0] CSD 309048\ 6] CSD 309059#[
2[7[ Data collection and structure re_nement of 0
Experimental data "a total of 3394 re~ections# were
collected at Tꢁ11921 K on a Siemens CCD "SMART#
di}ractometer in the range 1[8³1U³38[3> with mon!
Acknowledgements
Ä
ochromated MoKa radiation "lꢁ9[60962 A#[ This
We gratefully acknowledge support from the Fonds
der Chemischen Industrie[ Chemetall GmbH has pro!
vided a generous donation of lithium alkyls[ V[ P[ B[
includes a total of 1868 unique re~ections "Rintꢁ9[9016#[
All observed re~ections were used for determination of
the unit cell parameters[ The studied specimen was a
white single crystal with the dimensions 9[4×
9[3×9[1 mm[ Crystal data for 0 are as follows]
thanks the Sachsisches Ministerium fur Wissenschaft und
Ã
Ã
Kunst "SMWK# for _nancial support "Az[ 3!6420[49!93!
9250!87:7#[
¹
C03H19B09Cl1P1\ Mꢁ318[13\ space group P0 "No[ 1#\ a
Ä
Ä
ꢁ5[639"1# A\ b ꢁ 00[261"2# A\ c ꢁ 04[206"1#\ a ꢁ
095[72"1#>\ b ꢁ 099[99"1#>\ g ꢁ 091[38"1#>\ V ꢁ 0950[5"3#
2
−2
Ä
A \ at T ꢁ 119"1# K\ Z ꢁ 1\ Dc ꢁ 0[232 Mg m
\
References
F"999# ꢁ 325\ m"MoKa# ꢁ 9[344 mm−0\ no absorption
correction[
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ochromated MoKa "lꢁ9[60962 A# radiation[ This
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