CCDC reference numbers 280235 (3), 280236 (4) and 280237
(4·CH2Cl2).
3 days. After the morpholine had been removed in vacuo 25 ml
of degassed MeOH–H2O (1 : 3) was added, and the mixture
heated briefly to reflux and stirred for two days. Subsequently,
the mixture was filtered, dissolved in CH2Cl2 and the solution
dried with molecular sieves. The solvent was removed completely
and the colourless residue extracted into 10 ml of diethyl ether.
A colourless powder was obtained on storage of the solution
at −20 ◦C for several weeks. This was isolated and contained
2·CH2Ph as a major product according to 31P NMR spectroscopy.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b511833f
Synthesis of 3
1.0 ml (10 mmol) of BH3(SMe2) was added to a solution of 1.92 g
(4.3 mmol) of 2 in 40 ml of toluene. The solution was heated
to reflux briefly and stirred overnight. 120 ml of n-hexane was
added very quickly and the slightly turbid mixture was stored
at room temperature. Large, colourless crystals formed within a
Attempts to purify the crude product by recrystallisation failed.
1
31P{ H} NMR (161.9 MHz, C6D6), ABCD spin system: dA
=
+34.81(1) (m), dB = +29.15(1) (m), dC = −2.65(1) (m), dD = −8.22
few days, which were isolated and dried in vacuo. Yield: 1.22–
(m), 1JAC
Hz, 2JAD
=
=
232.2(2) Hz, 1JBD
13.5(2) Hz, 2JAB
=
250.8(2) Hz, 1JCD
19.1(2) Hz, 2JBC
=
260.4(2)
17.8(2) Hz.
◦
1
31
1.73 g (60–84%). Melting point: 153–155 C. H{ P,11B} NMR
(300.13 MHz, C6D6), d 1.76 [s, BH3 of (RP*,SP*,SP*,RP*)-( )-
3], 2.08 [s, BH3 of (RP*,RP*,RP*,RP*)-( )-3], 2.79 [s, CH2 of
(RP*,SP*,SP*,RP*)-( )-3], 3.01 [s, CH2 of (RP*,RP*,RP*,RP*)-( )-
=
=
Synthesis of 4
1
3], 6.7–8.3 (m, Ph); 13C{ H} NMR (100.16 MHz, C6D6), d 21.69
0.95 ml (9.5 mmol) of BH3(SMe2) was added to a solution of
2.63 g (4.9 mmol) of 5 in 50 ml of toluene. The mixture was
heated to reflux briefly and stirred for 1.5 h. Subsequently, the
solvent was removed completely, and the remaining colourless
solid dissolved in 10 ml of CH2Cl2. 20 ml of n-hexane was added
quickly, and the slightly turbid mixture was stored at −20 ◦C
for several days. Colourless crystals formed and were isolated
and dried in vacuo. The crystals contained approximately one
molecule of CH2Cl2 per formula unit according to 1H NMR
and elemental analysis. Yield: 1.40 g (44% ref. to 4·CH2Cl2 and
the amount of 5 supplied). Melting point: >180 ◦C (decomp.).
1H NMR (400.13 MHz, CDCl3), d 0.4–1.7 (br, 6H, BH3), 6.6–
1
2
[tt, JPC = 18.6 Hz, JPC = 5.4 Hz, CH2 of (RP*,RP*,RP*,RP*)-
1
2
( )-3], 27.11 [tt, JPC = ca. 17.8 Hz, JPC = ca. 3.3 Hz, CH2
of (RP*,SP*,SP*,RP*)-( )-3], 125–135 (several s and m, Ph);
1
31P{ H,11B} NMR (121.50 MHz, C6D6), (RP*,SP*,SP*,RP*)-( )-
1
1
ꢀ
ꢀ
ꢀ ꢀ
3: dA,A = +25.13(1) (m), dB,B = −35.08(1) (m), JAB = JA B
=
−188.5(3) Hz, 1JBB = −146.5(2) Hz, 2JAB = JA B = +35.1(1) Hz,
2
ꢀ
ꢀ
ꢀ
2
ꢀ
ꢀ
JAA = −15.3(2) Hz, (RP*,RP*,RP*,RP*)-( )-3: dA,A = +33.65(1)
(m), dB,B = −38.99(1) (m), 1JAB = JA B = −266.6(2) Hz, 1JBB
=
1
ꢀ
ꢀ
ꢀ
ꢀ
2
2
2
ꢀ
ꢀ
ꢀ
−172.6(2) Hz, JAB = JA B = +1.8(1) Hz, JAA = −32.0(2) Hz;
11B{ H} (96.29 MHz, C6D6), d 35.3 (br s, BH3); 31P MAS NMR
1
(202.45 MHz): d +21.3 (br, 2P, P–BH3), −23.1 [br, 1P, P–P(BH3)],
−39.0 [br, 1P, P–P(BH3)]. EI-MS, m/z (%): 473.9 (0.3) [M]+, 459.9
(0.7) [M − BH3]+, 368.8 (20) [M − 2BH3 − Ph]+, 229.9 (27) [M −
2BH3 − P2Ph2]+, 215.9 (7) [(P2Ph2)]+. Elemental analysis: found:
C 63.35, H 5.95, P 27.00; calc.: C 63.04; H 6.23; P 26.14%.
1
8.2 (m, 25H, Ph); 31P{ H} NMR (161.9 MHz, CDCl3), d 2–23
(overlapping m, P–BH3), −19 to −46 [overlapping m, P–P(BH3)
1
or P–P–P(BH3)]; 11B{ H} (128.4 MHz, CDCl3), +35 (br m, BH3).
Elemental analysis: found: C 56.96; H 5.07; P 24.84. calc.: C 57.02;
H 5.10; P 23.72%.
Synthesis of 3·Li
Acknowledgements
t
1.47 ml (1.7 mmol) of BuLi (1.14 M in n-hexane) was added to
0.79 g (1.7 mmol) of 3 in 40 ml of n-pentane. Then the mixture
was refluxed for 3.5 h. The resulting yellow–orange suspension
was filtered. The residue was dried in vacuo. The orange, very
air-sensitive powder was insoluble in hydrocarbons, but soluble
in THF. It was investigated by NMR spectroscopy. 1H NMR
(400.13 MHz, C7D8–THF), d 0.5–2.2 (br m, BH3), 2.51 (br m, CH),
We thank Dr Eberhard Matern (Karlsruhe University) for record-
ing the 11B-decoupled NMR spectra and valuable discussions.
Dr Winfried Bo¨hlmann is thanked for solid-state NMR mea-
surements, Dr Christina Thiele for recording the 2D 31P NMR
spectrum and Prof. Dr Stefan Berger for valuable discussions and
spectrometer time on the Bruker AVANCE 700 MHz spectrometer
(all University of Leipzig). Dr Alison J. Edwards (ANU, Canberra)
is thanked for assistance with the X-ray measurements of 3.
Support from the DAAD (PPP, DAAD/ARC, project number
313-ARC-XIV-00/37) and the Studienstiftung des Deutschen
Volkes (PhD grant for R. W.) is gratefully acknowledged.
1
6.3–8.5 (m, Ph); 31P{ H} NMR (161.9 MHz, C6D6–THF), d +90.2
ꢀ
ꢀ
[br m, PA,A of (RP*,RP*,RP*,RP*)-( )-3·Li], +39.1 [br m, PA,A of
ꢀ
(RP*,SP*,SP*,RP*)-( )-3·Li], +2.7 [m, PB,B of (RP*,RP*,RP*,RP*)-
ꢀ
( )-3·Li], −32.9 [m, PB,B of (RP*,SP*,SP*,RP*)-( )-3·Li], further
ꢀ
ꢀ
components: d +47.6 (m, PA,A of 2), +19.9 (m, PB,B of 2), −3.8 (m,
5), −48.2 [s, cyclo-(P4Ph4)], −62.1 (br s, unidentified species); 7Li
NMR (155.50 MHz, C7D8–THF), d 0.02 (s).
References
1 A. Schisler, PhD Dissertation, Universita¨t Leipzig, 2003.
Synthesis of 2·CH2Ph
2 (a) A. Schisler, U. Huniar, P. Lo¨nnecke, R. Ahlrichs and E. Hey-
Hawkins, Angew. Chem., 2001, 113, 4345; A. Schisler, U. Huniar,
P. L o¨nnecke, R. Ahlrichs and E. Hey-Hawkins, Angew. Chem., Int.
Ed., 2001, 40, 4217; (b) A. Schisler, P. Lo¨nnecke, T. Gelbrich and E.
Hey-Hawkins, Dalton Trans., 2004, 2895; (c) A. Schisler, P. Lo¨nnecke
and E. Hey-Hawkins, Inorg. Chem., 2005, 44, 461; (d) R. Wolf, A.
Schisler, P. Lo¨nnecke, C. Jones and E. Hey-Hawkins, Eur. J. Inorg.
Chem., 2004, 3277; (e) A. Schisler, P. Lo¨nnecke, E. Hey-Hawkins,
Chem.–Eur. J., manuscript in preparation.
0.53 ml (4.6 mmol) of benzyl chloride was added to a clear,
t
ice-cooled solution of 3·Li (freshly prepared from 3 and BuLi
according to the above procedure) in 15 ml toluene which
contained a few drops of THF in order to dissolve the lithium
salt. The solution turned pale and slightly turbid on addition
and was stirred overnight. The solvent was removed in vacuo
and 5 ml of morpholine was added. This mixture was stirred for
3 R. Wolf and E. Hey-Hawkins, Chem. Commun., 2004, 2626.
836 | Dalton Trans., 2006, 831–837
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The Royal Society of Chemistry 2006
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