Transition Metal Complexes of the Heterofunctional Phosphane o-Ph2PNHC6H4P(S)Ph2
FULL PAPER
ppm. FABϩ MS: m/z ϭ 510 [M]ϩ. Selected IR data (KBr): ν˜ ϭ tion was stirred for 30 min and then concentrated under reduced
3117 [w,ν(NϪH)], 1212 [s, ν(PϭO)], 924 [s, ν(PϪN)], 632 [vs, ν(Pϭ pressure to ca. 1Ϫ2 mL, and addition of petroleum ether (60Ϫ80
S)] cmϪ1
Method B: Ph2PNHC6H4P(S)Ph4 (1) (0.536 g, °C) precipitated an off-white solid. The product was collected by
.
1.086 mmol) was dissolved in boiling MeOH (30 mL) and the hot suction filtration, washed with petroleum ether (60Ϫ80 °C) (3 ϫ
solution was first cooled to room temperature and then stored at
10 mL) and dried in vacuo. Yield: 0.246 g, 88%. 1H NMR (CDCl3):
δ ϭ 8.47 (m, 1 H, NH), 7.90 (m, 1 H, aromatic), 7.83 (m, 22 H,
4 °C overnight to give 2 as a colourless powder, which was collected
by suction filtration, washed with ice-cold MeOH (2 ϫ 10 mL), aromatics), 6.82Ϫ6.68 (m, 2 H, aromatics) and 1.46 [d, 2J(31P-
and dried overnight in vacuo. Yield: 0.324 g, 59%. 31P{1H} NMR 1H) ϭ 11, 3J(195Pt-1H) ϭ 35 Hz, 6 H, PMe] ppm. FABϩ MS:
(CDCl3) and microanalytical data are similar to those of the mat-
erial generated by Method A.
m/z ϭ 898 [M]ϩ, 862 [M Ϫ Cl]ϩ, 827 [M Ϫ 2 Cl]2ϩ. Selected IR
data (KBr): ν˜ ϭ 3143 [w, ν(NϪH)], 912 [s, ν(PϪN)], 634 [m, ν(Pϭ
S)], 317 (w) ϩ 291 (w) [ν(PtCl)] cmϪ1
.
Ph2P(Se)NHC6H4P(S)Ph2 (3): Elemental selenium (0.085 g,
1.076 mmol) and 1 (0.534 g, 1.072 mmol) were stirred in warm (60
°C) toluene (20 mL) for 30 min. The solution was filtered through
Celite while still warm to remove a trace amount of unchanged
selenium. The Celite was washed with warm (60 °C) toluene (2 ϫ
10 mL). The filtrate and washings were combined and reduced in
volume to ca. 15 mL, and the resulting colourless solid was col-
lected by suction filtration, washed with toluene (2 ϫ 5 mL) and
ice-cold diethyl ether (2 ϫ 5 mL), and dried in vacuo. Yield:
0.524 g, 85%. 1H NMR (CDCl3): δ ϭ 8.34 [br. d, 2J(31P-1H) ϭ
8 Hz, 1 H, NH], 7.79Ϫ7.68 (m, 4 H, aromatics), 7.63Ϫ7.24 (m, 18
H, aromatics), 6.85 (m, 1 H, aromatic), 6.77Ϫ6.67 (m, 1 H, aro-
matic) ppm. FABϩ MS: m/z ϭ 573 [M]ϩ. Selected IR data (KBr):
ν˜ ϭ 3098 [s, ν(NϪH)], 925 [vs, ν(PϪN)], 631 [s, ν(PϭS)], 548 [vs,
[AuCl{Ph2PNHC6H4P(S)Ph2-P}] (7): To a stirred solution of
[AuCl(tht)] (0.045 g, 0.140 mmol) in CH2Cl2 (4 mL) was added 1
(0.070 g, 0.142 mmol) as a solid in one portion. The mixture was
stirred for 1 h and filtered through a Celite plug to remove a small
amount of grey insoluble material. Diethyl ether (35 mL) was ad-
ded slowly until a white solid precipitated. The product was col-
lected by suction filtration, washed with diethyl ether (2 ϫ 10 mL),
and dried in vacuo. Yield: 0.085 g, 83%. 1H NMR (CDCl3): δ ϭ
8.00 [br. d, 2J(31P-1H) ϭ 3 Hz, 1 H, NH], 7.71Ϫ7.29 (m, 21 H,
aromatics), 7.14 (m, 1 H, aromatic), 6.95 (m, 1 H, aromatic) and
6.71 (m, 1 H, aromatic) ppm. FABϩ MS: m/z ϭ 726 [M]ϩ, 691/692
[M Ϫ Cl]ϩ. Selected IR data (KBr): ν˜ ϭ 3109 [m, ν(NϪH)], 927
[m, ν(PϪN)], 632 [s, ν(PϭS)], 339 [w, ν(AuϪCl)] cmϪ1
.
ν(PϭSe)] cmϪ1
.
cis-[PdCl2{Ph2PNHC6H4P(S)Ph2-P}2] (8): To a stirred solution of
[PdCl2(cod)] (0.078 g, 0.273 mmol) in CH2Cl2 (2.5 mL) was added
1 (0.273 g, 0.553 mmol) as a solid in one portion. The resulting
clear pale yellow solution was stirred for 10 min, and the pale yel-
low precipitate was collected by suction filtration, washed with
CH2Cl2 (2 ϫ 2 mL) and diethyl ether (3 ϫ 10 mL), and dried in
vacuo. Yield: 0.309 g, 97%. Selected IR data (KBr): ν˜ ϭ 3108 [br,
ν(NϪH)], 919 [vs, ν(PϪN)], 632 [vs, ν(PϭS)], 318 (w) ϩ 298 (w)
[PdCl(η3-C3H5){Ph2PNHC6H4P(S)Ph2-P}] (4): To a stirred toluene
(15 mL) suspension of [Pd(µ-Cl)(η3-C3H5)]2 (0.115 g, 0.316 mmol)
was added in one portion solid 1 (0.312 g, 0.632 mmol). The mix-
ture was stirred for 3 h to give a light, cream-coloured precipitate.
The solvent volume was reduced in vacuo to ca. 5 mL and light
petroleum ether (40Ϫ60 °C) (20 mL) was added to further precipit-
ate the product, which was collected by suction filtration, washed
with light petroleum ether (40Ϫ60 °C) (2 ϫ 15 mL), and dried in
vacuo. Yield: 0.354 g, 83%. 1H NMR (CDCl3): δ ϭ 8.02 (s, 1 H,
NH), 7.81Ϫ7.24 (m, 22 H, aromatics), 6.82Ϫ6.73 (m, 2 H, aro-
matic), 5.36 (m, 1 H, allyl), 4.64 (m, 1 H, allyl), 3.59 (m, 1 H, allyl),
3.04 (m, 1 H, allyl), 2.39 (m, 1 H, allyl) ppm. FABϩ MS: m/z ϭ
676 [M]ϩ, 641 [M Ϫ Cl]ϩ, 600 [M Ϫ Cl Ϫ C3H5]2ϩ. Selected IR
data (KBr): ν˜ ϭ 3144 [br, ν(NϪH)], 912 [m, ν(PϪN)], 632 [m, ν(Pϭ
[ν(PdϪCl)] cmϪ1
.
cis-[PtCl2{Ph2PNHC6H4P(S)Ph2-P}2] (9): This compound was pre-
pared in the same way as 8 using [PtCl2(cod)] (0.051 g, 0.136 mmol)
in CH2Cl2 (2.5 mL) and 1 (0.138 g, 0.280 mmol). The resulting
clear pale yellow solution was stirred for 2 h, and the product was
precipitated by slow addition of diethyl ether (15 mL). The crude
product was immediately redissolved in CH2Cl2 (5 mL) and repre-
cipitated by slow addition of diethyl ether (30 mL), washed with
ice-cold CH2Cl2/diethyl ether (1:1) (4 mL) and diethyl ether (3 ϫ
10 mL). The resulting white solid was collected by suction filtration
S)] cmϪ1
.
[PtCl(η3-C3H5){Ph2PNHC6H4P(S)Ph2-P}] (5): To a stirred THF
(20 mL) suspension of [Pt(µ-Cl)(µ-η2:η1-C3H5)]4 (0.153 g,
1
and dried in vacuo. Yield: 0.150 g, 88%. H NMR (CD2Cl2): δ ϭ
0.141 mmol) was added in one portion solid
1 (0.280 g,
7.90 [br. d, 2J(31P-1H) ϭ 7 Hz, 2 H, NH], 7.76Ϫ7.08 (m, 44 H,
aromatics) and 6.71Ϫ6.58 (m, 4 H, aromatics) ppm. FABϩ MS:
m/z ϭ 1217/8 [M Ϫ Cl]ϩ, 1182 [M Ϫ 2 Cl]2ϩ. Selected IR data
(KBr): ν˜ ϭ 3125 [m, ν(NϪH)], 920 [s, ν(PϪN)], 634 [s, ν(PϭS)],
311 (w) ϩ 290 (w) [ν(PtϪCl)] cmϪ1. The product was consistently
contaminated with an impurity (ca. 4Ϫ5%) observed as two singlets
in the 31P{1H} NMR at δ(P) ϭ 40.2 and 40.8 ppm, thought to be
trans-[PtCl2{Ph2PNHC6H4P(S)Ph2-P}2].
0.568 mmol). The mixture was stirred for 6 h to give a dirty yellow
solution that was filtered through a Celite plug to remove a small
quantity of dark insoluble material. The resulting very pale yellow
solution was reduced in vacuo to ca. 4Ϫ5 mL, and light petroleum
ether (40Ϫ60 °C) (25 mL) was added to precipitate the product as
a cream-coloured powder, which was collected by suction filtration,
washed with light petroleum ether (40Ϫ60 °C) (2 ϫ 10 mL), and
dried in vacuo. Yield: 0.379 g, 88%. 1H NMR (CDCl3): δ ϭ 8.07 [s,
3J(195Pt-1H) ϭ 47 Hz, 1 H, NH], 7.80Ϫ7.19 (m, 22 H, aromatics),
6.78Ϫ6.71 (m, 2 H, aromatic), 4.76 (m, 1 H, allyl), 4.28 (m, 1 H,
allyl), 2.92 (m, 2 H, allyl) 1.87 [m, 3J(195Pt-1H) ϭ 78 Hz, 1 H, allyl]
ppm. FABϩ MS: m/z ϭ 765 [M]ϩ, 730 [M Ϫ Cl]ϩ, 689 [M Ϫ Cl Ϫ
C3H5]2ϩ. Selected IR data (KBr): ν˜ ϭ 3142 [br, ν(NϪH)], 912 [s,
trans-[PtClMe{Ph2PNHC6H4P(S)Ph2-P}2] (10): This was prepared
in the same way as 8 using [PtClMe(cod)] (0.093 g, 0.263 mmol) in
CH2Cl2 (4 mL) and 1 (0.270 g, 0.547 mmol). The white solid was
collected by suction filtration, washed with CH2Cl2 (2 ϫ 2 mL)
and diethyl ether (3 ϫ 10 mL) and dried in vacuo. Yield: 0.318 g,
98%. Selected IR data (KBr): ν˜ ϭ 3128 [br, ν(NϪH)], 911 [vs,
ν(PϪN)], 634 [s, ν(PϭS)], 298 [w, ν(PtϪCl)] cmϪ1
.
ν(PϪN)], 633 [vs, ν(PϭS)], 288 [w, ν(PtϪCl)] cmϪ1
.
cis-[PtCl2{Ph2PNHC6H4P(S)Ph2-P}(PMe2Ph)] (6): To a stirred
CH2Cl2 (25 mL) solution of [{PtCl(µ-Cl)(PMe2Ph)}2] (0.126 g,
cis-[PtMe2{Ph2PNHC6H4P(S)Ph2-P}2] (11): This was prepared in
0.156 mmol) was added dropwise over 10 min a CH2Cl2 (20 mL) the same way as 8 using [PtMe2(cod)] (0.070 g, 0.210 mmol) in tolu-
solution of 1 (0.154 g, 0.312 mmol). The resulting pale yellow solu-
ene (4 mL) and 1 (0.210 g, 0.43 mmol). The resulting clear pale
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