ꢀ
vacuum, the residual white solid washed thrice with diethyl ether
and finally dried under vacuum. The residue was then dissolved in
5 ml of acetonitrile, triethylamine (0.35 ml, 2.5 mmol) was added,
and the solution stirred under slight vaccum (12 torr) for 15 min.
All volatiles were finally evaporated under vacuum and the residue
recrystallised at −28 ◦C from a concentrated solution in THF.
(s, p-C), 129.1 (pseudo-t, JPC = 9.6 Hz, o-C), 128.9 (pseudo-t,
ꢀ
JPC = 10.2 Hz, o-C), 119.5 (m, C6H3), 118.9 (m, C6H3), 113.2
1
(s, C6H3), 109.6 (m, C6H3), 30.8 (d, 1JPC = 0.8 Hz, CH2). 31P{ H}
NMR (CDCl3): d = 2.9 (1JP-107/109Ag = 585/507 Hz). 109Ag NMR
(CDCl3): d = 645. 1H NMR (DMF-d7): d = 8.00 to 7.86 (m, 12 H,
3
Ph), 7.68 (m, 4 H, Ph), 7.58 (m, 4 H, Ph), 6.72 (broad d, JHH
=
7.7 Hz, 2 H, C6H3), 6.57 (dd, 3JHH = 7.7/7.7 Hz, 2 H, C6H3), 6.48
Triethylammonium bis[diphenylphosphine{benzo-(1,3)-dioxa-4-
methyl}]-2-borate (6[Et3NH]). Yield 346 mg (83%), mp 92 ◦C. El-
emental analysis: C44H46BNO4P2 (725.6): Calcd C 72.83, H 6.39,
N 1.93, found C 70.83, H 6.78, N 1.70%. 1H NMR (CD3CN): d =
7.6 to 7.26 (m, 20 H, Ph), 6.8 (broad, 1 H, NH), 6.44 to 6.34 (m,
6 H, C6H3), 3.51 (dd, 2 H, 2JHH = 13.9 Hz, 2JPH = 0.9 Hz, CH2),
3.44 (d, 2 H, 2JPH = 13.9 Hz, CH2), 3.13 (q, 6 H, 3JHH = 7.3 Hz,
3
2
(broad d, JHH = 7.8 Hz, 2 H, C6H3), 4.09 (m, JHH = 13.3 Hz,
ꢀ
3JHAg = 7 Hz, JPH = 14 Hz, 2 H, CH2), 3.95 (d pseudo-t, 2JHH
=
ꢀ
13.3 Hz, JPH = 4 Hz, 2 H, CH2). 31P{ H} NMR (DMF-d7): d =
1
3.0 (1JP-107/109Ag = 571/494 Hz). 109Ag NMR (DMF-d7): d = 702.
Synthesis of [(7)2Ag2] (9)
3
NCH2), 1.23 (t, 9 H, JHH = 7.4 Hz, CH3). 11B NMR (CD3CN):
AgOTf (117 mg, 0.46 mmol) was added to a stirred solution of
7[Et3NH] (330 mg, 0.46 mmol) in DMF (13 ml). The stirring was
continued for 1 h. Addition of diethyl ether (40 ml) produced
a white precipitate which was collected by filtration and dried
at 50 ◦C under vacuum (0.001 mbar) for 3 h to give 471 mg
(70%) of pure product of mp 180 ◦C. Elemental analysis:
C76H60Ag2B2O8P4·2DMF (1460.15): calcd C 61.22, H 4.64, N 1.74,
found C 60.03, H 4.83, N 2.27%. ESI-MS (positive mode): m/z =
1
d = 14.3 (s). 13C{ H} NMR (CD3CN): d = 151.3 (d, JPC = 1.2 Hz,
1
C6H3), 149.9 (d, JPC = 4.2 Hz, C6H3), 139.5 (d, JPC = 16.5 Hz,
1
2
i-C), 139.2 (d, JPC = 16.3 Hz, i-C), 132.78 (d, JPC = 18.9 Hz,
m-C), 132.76 (d, 2JPC = 18.9 Hz, m-C), 128.53 (s, p-C), 128.48 (s,
2
2
p-C), 128.40 (d, JPC = 6.5 Hz, o-C), 128.38 (d, JPC = 6.7 Hz,
o-C), 118.9 (d, JPC = 8.4 Hz, C6H3), 117.1 (d, JPC = 1.5 Hz, C6H3),
105.9 (br, C6H3), 47.0 (s, NCH2), 27.5 (d, 1JPC = 13.4 Hz, PCH2),
1
8.2 (s, NCCH3). 31P{ H} NMR (CD3CN): d = −13.2.
1485.13 [MNa]+, 754.06 [MNa2]2+. H NMR (DMF-d7): d = 7.8
1
3
to 7.3 (m, 40 H, Ph), 6.42 (broad, 4 H, C6H3), 6.34 (d, JHH
=
Triethylammonium bis[diphenylphosphine{benzo-(1,3)-dioxa-5-
methyl}]-2-borate (7[Et3NH). Yield 372 mg (90%), mp
197 ◦C. Elemental analysis: C44H46BNO4P2 (725.6): Calcd C 72.83,
H 6.39, N 1.93, found C 72.90, H 6.39, N 1.90%. 1H NMR
(CD3CN): d = 7.50 to 7.40 (m, 8 H, C6H5), 7.40 to 7.30 (m,
12 H, C6H5), 6.8 (broad, 1 H, NH), 6.37 to 6.30 (broad m, 6 H,
C6H3), 3.37 (s, 4 H, CH2), 3.08 (q, 6 H, 3JHH = 7.3 Hz, NCH2), 1.18
8.1 Hz, 4 H, C6H3), 6.24 (dd, 3JHH = 7.7, 7.7 Hz, 4 H, C6H3), 3.76
(broad, 8 H, CH2). 11B{ H} NMR (DMF-d7): d = 14.6. 31P{ H}
1
1
NMR (DMF-d7): d = 12.8 (broad).
Crystal structure studies
Single-crystal X-ray diffraction studies were carried out either on
a Nonius Kappa-CCD diffractometer at 100(2) or 123(2) K using
3
(t, 9 H, JHH = 7.3 Hz, NCCH3). 11B NMR (CD3CN): d = 14.3
1
(s). 13C{ H} NMR (CD3CN): d = 152.5 (d, JPC = 1.3 Hz, C6H3),
˚
MoKa radiation (k = 0.71073 A). Direct methods (SHELXS-
151.0 (d, JPC = 2.7 Hz, C6H3), 140.2 (d, 1JPC = 17.3 Hz, i-C), 133.8
(d, 3JPC = 18.6 Hz, m-C), 129.6 (s, p-C), 129.3 (d, 2JPC = 6.5 Hz,
o-C), 127.4 (d, JPC = 8.3 Hz, C6H3), 119.3 (d, JPC = 7.5 Hz, C6H3),
110.3 (d, JPC = 6.7 Hz, C6H3), 108.3 (s, C6H3), 47.9 (s, NCH2),
9721) were used for structure solution and refinement (SHELXL-
97,22 full-matrix least-squares on F2). Absorption corrections were
applied for 4 (empirical), 7 and 8,23 and H atoms were refined using
a riding model.
1
35.6 (d, 1JPC = 13.6 Hz, PCH2), 9.12 (s, NCCH3). 31P{ H} NMR
Compound
4. Colourless
crystals,
([C38H34AgO4P2]+-
(CD3CN): d = −10.2.
[CF3SO3]−·CH2Cl2·C3H7NO), M = 1031.5, crystal size 0.40 ×
0.24 × 0.12 mm, monoclinic, space group P21/n (No. 14): a =
Synthesis of [(6)Ag] (8)
◦
˚
˚
˚
−3
13.818 (1) A, b = 22.343(2) A, c = 15.085(1) A, b = 104.46(1) ,
3
˚
V = 4509.7(6) A , Z = 4, q(calcd) = 1.519 Mg m , F(000) = 2104,
l = 0.747 mm−1, 37390 reflections (2 hmax = 50◦), 7908 unique
[Rint = 0.047], 561 parameters, 27 restraints, R1 (I >2r(I)) =
0.059, wR2 (all data) = 0.160, largest difference peak and hole
AgOTf (46 mg, 0.18 mmol) was added to a stirred solution of
6[Et3NH] (130 mg, 0.18 mmol) in DMF (5 ml). The stirring was
continued for 1 h. Addition of diethyl ether (60 ml) produced
a white precipitate which was collected by filtration and dried
at 40 ◦C under vacuum (0.001 mbar) for 3 h to give 92.14 mg
(70%) of pure product of mp 253 ◦C. Single crystal were obtained
by recrystallisation from DMF : diethyl ether (1 : 1) at room
temperature. Elemental analysis: C38H30AgBO4P2 (731.28): calcd
C 62.41, H 4.14, found C 60.81, H 4.12, N 0.25%. ESI-MS: m/z =
733.08 [MH]+, 755.07 [MNa]+. 1H NMR (CDCl3): d = 7.6 to 7.22
(m, 20 H, Ph), 6.80 (broad d, 3JHH = 7.7 Hz, 2 H, C6H3), 6.53 (dd,
−3
˚
1.391 and −2.510 e A .
Compound
5. Colourless
crystals,
([C38H34AgO4P2]+-
[CF3SO3]−·2THF), M = 1017.7, crystal size 0.15 × 0.10 ×
0.05 mm, monoclinic, space group P21/n (No. 14): a = 14.3659(3)
◦
˚
˚
˚
A, b = 16.1257(4) A, c = 19.8458(6) A, b = 92.338(1) , V =
3
−3
˚
4593.7(2) A , Z = 4, q(calcd) = 1.472 Mg m , F(000) = 2096,
l = 0.621 mm−1, 25126 reflections (2 hmax = 50◦), 8092 unique
[Rint = 0.046], 580 parameters, 110 restraints, R1 (I >2r(I)) =
0.032, wR2 (all data) = 0.061, largest difference peak and hole
3
3JHH = 7.7 Hz, 2 H, C6H3), 6.21 (broad d, JHH = 7.8 Hz, 2 H,
ꢀ
C6H3), 3.95 (d of pseudo-t, 2JHH = 13.3 Hz, JPH = 4.6 Hz, 2H,
ꢀ
Hc), 3.51 (dd pseudo-t, 2JHH = 13.3 Hz, 3JHAg = 7.5 Hz, JPH
=
1
−3
˚
0.499 and −0.349 e A .
1
12.3 Hz, 2 H, Ht). 11B{ H} NMR (CDCl3): d = 14.3. 13C{ H}
NMR (CDCl3): d = 151.4 (m, C6H3), 149.0 (m, C6H3), 133.1 (m,
Compound 6[Et3NH]. Colourless crystals, ([Et3NH]+[C38H30-
ꢀ
ꢀ
JPC = 16.2 Hz, 4JAgC = 2.4 Hz, m-C), 132.5 (m, JPC = 15.3 Hz,
BO4P2]−·DME), M = 815.7, crystal size 0.40 × 0.30 × 0.20 mm,
4JAgC = 2.4 Hz, m-C), 132.2 (i-C), 131.9 (i-C), 131.0 (s, p-C), 129.8
3912 | Dalton Trans., 2007, 3906–3913
triclinic, space group P1 (No. 2): a = 16.3386(2) A, b = 16.3500(2)
˚
This journal is
The Royal Society of Chemistry 2007
©