S. Burck et al. · Activation of Polarized Phosphorus-Phosphorus Bonds by Alkynes
71
1
tion of 12 as main product was verified by 31P NMR [δ = 3JHH = 7.2 Hz, CH3). – 13C{ H} NMR (CDCl3): δ = 162.4
3
3
84.3 (d, JPP = 220 Hz), −13.3 (d, JPP = 220 Hz)]. (Cy- (dd, 3JPC = 32.0 Hz, 2JPC = 3.4 Hz, C=O), 143.6 (d, 1JPC
=
=
clooctadiene)palladium dichloride (115 mg, 0.4 mmol) was 3.5 Hz), 139.8 (broad s), 138.2 (dd, JPC = 16.9 Hz, 3JPC
1
then added, the solution stirred for further 10 h, and finally 2.1 Hz, =C), 137.5 (d, JPC = 6.5 Hz), 135.3 (broad s), 133.9
3
evaporated to dryness. The residue was treated with toluene (d, JPC = 11.4 Hz), 132.5 (d, JPC = 2.9 Hz), 130.9 (broad
(4 mL), the resulting suspension filtered, and the remaining s), 129.4 (d, JPC = 12.1 Hz), 128.9 (broad s), 128.2 (d, JPC
=
1
2
solid residue of 13 dried in vacuum; yield 272 mg (85 %). – 1.3 Hz), 127.0 (dd, JPC = 61.9 Hz, JPC = 0.8 Hz, =CH),
2
M. p. 264 ◦C. – 1H NMR (CD3CN): δ = 7.70 – 7.60 (m, 122.8 (d, JPC = 3.4 Hz, N-CH), 63.2 (s, OCH2), 21.5 (s,
3
1
4 H, o-C6H5), 7.50 – 7.00 (m, 12 H), 6.40 (d, 2 H, JPH
=
o-CH3), 20.7 (s, o-CH3), 14.5 (s, CH3). – 31P{ H} NMR
14.2 Hz, N-CH), 3.86 (s, 3 H, OCH3), 3.56 (s, 3 H, OCH3), (CDCl3): δ = 108.6 (d, 2JPP = 20.0 Hz, N2P), 62.2 (d, 2JPP
=
2.63 (s, 6 H, o-CH3), 2.25 (s, 6 H, o-CH3). – 13C{ H} NMR 20.0 Hz, PPh2). – MS: (EI, 70 eV, 480 K): m/z (%) = 756.1
1
(CD3CN): δ = 163.1 (d, JPC = 61 Hz, C=O), 162.9 (d, JPC
55 Hz, C=O), 138.6 (d, JPC = 3.6 Hz), 137.3 (d, JPC
=
=
(0.1) [M]+, 295.1 (14) [C17H26O2PdCl2]+, 249.1 (100). –
C35H36N2O2P2PdCl2 (755.96) · CH3CN: calcd. C 56.57,
6.6 Hz), 135.9 (d, JPC = 1.9 Hz), 134.3 (d, JPC = 11.9 Hz), H 5.36, N 3.38; found C 56.08, H 5.23, N 3.28.
133.0 (d, JPC = 3.1 Hz), 130.1 (d, JPC = 1.0 Hz), 129.0 (dd,
JPC = 8.2 Hz, 1.8 Hz), 128.9 (d, JPC = 11 Hz), 128.2 (s),
(Z-2-[1,3-Bis-(2ꢀ,6ꢀ-dimethylphenyl)-2,3-dihydro-1H-1,3,2-
diazaphospholyl]-3-diphenylphosphanyl-acrylic acid ethyl
128.1 (d, JPC = 1.7 Hz), 123.1 (d, JPC = 2.9 Hz, N-CH), 53.6
ester)dichloro platinum(II) (16)
(s, OCH3), 53.3 (s, OCH3), 20.4 (s, CH3), 20.3 (s, CH3). –
31P{ H} NMR (CD3CN): δ = 105.9 (d, JPP = 17.4 Hz,
1
Yield 284 mg (87 %). – M. p. 151 ◦C. – 1H NMR (C6D6):
2
N2P), 77.5 (d, JPP = 17.4 Hz, PPh2). – C36H36N2O4P2PdCl2
(799.97)·0.5 CH3CN: calcd. C 54.16, H 4.61, N 4.27; found
54.17, H 4.61, N 4.37.
δ = 7.46 – 7.33 (m, 4 H, o-C6H5), 7.18 (dd, 1 H, JPH
=
65.4 Hz, 3JPH = 11.7 Hz, =CH), 6.90 – 6.68 (m, 12 H), 5.62
(d, 2 H, 3JPH = 15.5 Hz, N-CH), 4.03 (q, 2 H, 3JHH = 7.1 Hz,
CH2), 2.90 (s, 6 H, o-CH3), 2.13 (s, 6 H, o-CH3), 0.93 (t,
General procedure for the reaction of 4 with metal(II) salts
3 H, JHH = 7.1 Hz, CH3). – 31P{ H} NMR (C6D6): δ =
3
1
2
1
Ligand 4 (231 mg, 0.4 mmol) and one equiv. of the
appropriate metal salt (anhydrous NiCl2, (COD)PdCl2, or
(COD)PtCl2) were mixed with THF (10 mL) and the sus-
pension diluted with CH3CN until all solids had dissolved.
Storing the formed clear solutions at −20 ◦C gave red crys-
tals of the complexes which were collected by filtration and
dried in vacuum.
86.7 (d, JPP = 3.7 Hz, JPtP = 4720 Hz, N2P), 35.7 (d,
1
1
2JPP = 3.7 Hz, JPtP = 3548 Hz, PPh2). – 195Pt{ H} NMR
(C6D6): δ = −4420 (dd, 1JPtP = 4720, 3548 Hz). – MS (EI,
70 eV, 430K): m/z (%) = 844.1 (0.4) [M]+, 808.1 (0.3) [M–
Cl]+, 773.1 (0.6) [M–2 Cl]+. – C35H36N2O2P2PtCl2: calcd.
C 49.77, H 4.30, N 3.32; found C 49.76, H 4.51, N 3.56.
(Z-2-(1,3-dineopentyl-1H-benzo[1,3,2]diazaphosphol-
2(3H)-yl)-3-(diphenylphosphino)acrylic acid ethyl ester) (8)
and its dichloropalladium complex 17
(Z-2-[1,3-Bis-(2ꢀ,6ꢀ-dimethylphenyl)-2,3-dihydro-1H-1,3,2-
diazaphospholyl]-3-diphenylphosphanyl-acrylic acid ethyl
ester)dichloro nickel(II) (14)
Ethyl propiolate (96 mg, 0.97 mmol) was added to a
stirred solution of 6 (450 mg, 0.97 mmol) in THF (10 mL),
and the mixture was stirred for 0.5 h at r. t. after the addition
was complete. The formation of 8 as the main product was
Yield 252 mg (89 %). – M. p. 145 ◦C. – 1H NMR (C6D6):
3
δ = 7.46 (d, broad, JPH = 7.5 Hz, 4 H, o-C6H5), 6.98 –
6.70 (m, 12 H), 5.60 (s, broad, 2 H N-CH), 3.91 (q, 2 H,
3JHH = 7.2 Hz, CH2), 2.98 (s, broad, 6 H, o-CH3), 2.12 (s,
verified by 31P NMR [δ = 94.4 (d, JPP = 166 Hz), −25.4
2
3
2
broad, 6 H, o-CH3), 0.83 (t, 3 H, JHH = 7.2 Hz, CH3). –
(d, JPP = 166 Hz)]. A solution of (COD)PdCl2 (270 mg,
31P{ H} NMR (C6D6): δ = 112.2 (broad s, N2P), 50.6
1
0.97 mmol) in CH2Cl2 (25 mL) was then added dropwise.
The solution was stirred for further 0.5 h after the addi-
tion was complete and was then evaporated to dryness. The
residue was extracted with diethyl ether (20 mL), the result-
ing suspension filtered, and the remaining red solid residue
of crude 17 recrystallized at −20 ◦C from Et2O/CH2Cl2
(1 : 1), yield 380 mg (53 %). – 1H NMR (C6D6): δ = 7.94
(broad s, PPh2). – MS (EI, 70 eV, 430 K): m/z (%) = 576.3
(2) [M–NiCl2]+, 295.1 (100) [M–C17H16O2PNiCl2]+. –
C35H36N2O2P2NiCl2 (708.23)·C4H8O: calcd. C 60.03,
H 5.68, N 3.59; found C 60.72, H 5.78, N 3.46.
(Z-2-[1,3-Bis-(2ꢀ,6ꢀ-dimethylphenyl)-2,3-dihydro-1H-1,3,2-
diazaphospholyl]-3-diphenylphosphanyl-acrylic acid ethyl
ester)dichloro palladium(II) (15)
2
3
(m, 4 H, o-C6H5), 7.95 (dd, 1 H, JPH = 73.4 Hz, JPH
10.7 Hz, =CH), 7.66 (m, 2 H, p-C6H5), 7.56 (m, 4 H, m-
=
Yield 253 mg (84 %). – M. p. 162 ◦C. – 1H NMR (CDCl3): C6H53), 6.97 (m, 2 H, C6H4), 6.94 (m, 2 H, C6H4), 4.04 (q,
3
δ = 7.27 – 6.78 (m, 14 H), 6.69 – 6.53 (m, 2 H), 5.95 (d, 2 H, 2 H, JHH = 7.1 Hz, CH2), 3.81 (dd, 2 H, JPH = 18.1 Hz,
3JPH = 13.9 Hz, N-CH), 4.12 (q, 2 H, 3JHH = 7.2 Hz, CH2), 2JHH = 15.7 Hz, CH2), 3.43 (dd, 2 H, JPH
=
2JHH
=
=
3
3
2.47 (s, 6 H, o-CH3), 1.80 (s, 6 H, o-CH3), 1.11 (t, 3 H, 15.4 Hz, CH2), 0.89 (s, 18 H, CH3), 0.74 (t, 3 H, JHH
Unauthenticated
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