570 Organometallics, Vol. 18, No. 4, 1999
Gerisch et al.
in methylene chloride (3 mL) was added triphenylphosphine
(168 mg, 0.64 mmol) or triphenylarsine (196 mg, 0.64 mmol)
at room temperature, affording a light green solution within
1 min. After 2 h diethyl ether (10 mL) was added and the
precipitate so formed was filtered off, washed with diethyl
ether, and dried briefly in vacuo. 4a (L ) PPh3, R ) Me):
Yield: 221 mg, 85%. Mp (dec): 276-279 °C. Anal. Calcd for
ν(CO) 2071vw (11a ), 1668s (12), ν(PtCl) 302vw, 281vw, 253vw,
245vw cm-1
.
[P t2(COR )2(µ-Cl)(µ-d p p m )2]Cl (6). Complexes 6 were
prepared according to the procedure described for 4 using 2
equiv of bis(diphenylphosphino)methane (123 mg, 0.32 mmol)
instead of triphenylphosphine. 6a (R ) Me): Yield: 158 mg,
75%. Mp (dec): 217-219 °C. Anal. Calcd for C54H50Cl2O2P4-
Pt2 (1315.94): C 49.29; H 3.83; Cl 5.39. Found: C 48.83; H
3.87; Cl 5.43. IR (CsBr): ν(CO) 1656, 1650 cm-1. 1H NMR (200
MHz, 293 K, CDCl3): δ 1.42 (s, 6H, CH3), 3.96-4.38 (m, 4H,
C
38H33ClOP2Pt (798.16): C 57.18; H 4.17; Cl 4.44. Found: C
57.19; H 4.24; Cl 4.82. IR (CsBr): ν(CO) 1654, ν(PtCl) 255 cm-1
.
1H NMR (200 MHz, CDCl3): δ 1.18 (s+d, 3H, 3J (PtH) ) 13
Hz, CH3), 7.40 (m, 18H, m-, p-CH), 7.76 (m, 12H, o-CH). 13C
1
CH2), 7.39 (m, 24H, m-, p-CH), 7.75 (m, 16H, o-CH). H NMR
3
NMR (50 MHz, CDCl3): δ 44.2 (t, J (PC) ) 6 Hz, CH3), 128.2
(500 MHz, 253 K, CD2Cl2): δ 1.38 (s, 6H, CH3), 3.99 (m, 2H,
CH2), 4.25 (m, 2H, CH2), 7.37-7.82 (m, CH, 40H). 13C NMR
(126 MHz, CDCl3): δ 29.9 (“q”, N ) 30 Hz, CH2), 42.9 (t+d,
2J (PtC) ) 225 Hz, 3J (PC) ) 4 Hz, CH3), 128.0-133.7 (phenyl-
C), 200.5 (s+d, 1J (PtC) ) 962 Hz, CO). 31P NMR (81 MHz,
CDCl3): δ 7.3 (s+m, 1J (PtP) ) 3447 Hz, 3J (PtP) ) 56 Hz,
(“t”, N ) 11 Hz, m-CH), 130.3 (“t”, N ) 28 Hz, i-C), 130.7 (p-
CH), 134.9 (“t”, N ) 12 Hz, o-CH), 218.4 (t, 2J (PC) ) 6 Hz,
1
CO). 31P NMR (81 MHz, CDCl3): δ 20.9 (s+d, J (PtP) ) 3480
Hz). 4b (L ) PPh3, R ) Et): Yield: 228 mg, 78%. Mp (dec):
279-281 °C. Anal. Calcd for C39H35ClOP2Pt (812.19): C 57.68;
H 4.34; Cl 4.56. Found: C 57.54; H 4.42; Cl 4.66. IR (CsBr):
4
2
2J (PP) ) 30/48 Hz, J (PP) < 1 Hz, J (PtPt) ) 474 Hz). 6b (R
) Et): Yield: 146 mg, 68%. Mp (dec): 214-216 °C. Anal. Calcd
for C56H54O2Cl2P4Pt2 (1344.00): C 50.00; H 4.05; Cl 5.28.
1
ν(CO) 1658, ν(PtCl) 253 cm-1. H NMR (200 MHz, CDCl3): δ
-0.13 (t, 3H, CH3), 1.53 (q, 2H, CH2), 7.39 (m, 18H, m-, p-CH),
7.75 (m, 12H, o-CH). 13C NMR (50 MHz, CDCl3): δ 8.2 (s+d,
3J (PtC) ) 19 Hz, CH3), 51.2 (t+d, 3J (PC) ) 6 Hz, 2J (PtC) )
186 Hz, CH2), 128.2 (“t”, N ) 11 Hz, m-CH), 130.4 (“t”, N ) 28
Hz, i-C), 130.6 (p-CH), 134.9 (“t”, N ) 12 Hz, o-CH), 218.8 (t+d,
2J (PC) ) 6 Hz, 1J (PtC) ) 917 Hz, CO). 31P NMR (81 MHz,
Found: C 49.83; H 3.93; Cl 5.41. IR (CsBr): ν(CO) 1656 cm-1
.
1H NMR (200 MHz, 293 K, CDCl3): δ -0.03 (t, 6H, CH3), 1.62
(q, 4H, CH2), 4.04 (s br, 2H, PCH2), 4.23 (s br, 2H, PCH2), 7.39
1
(m, 24H, m-, p-CH), 7.75 (m, 16H, o-CH). H NMR (500 MHz,
253 K, CD2Cl2): δ -0.03 (t, 6H, CH3), 1.62 (q, 4H, CH2), 4.03
(m, 2H, PCH2), 4.22 (m, 2H, PCH2), 7.26-7.80 (m, CH, 40H).
13C NMR (126 MHz, CDCl3): δ 8.6 (s+d, 3J (PtC) ) 22 Hz, CH3),
30.5 (m, PCH2), 50.0 (s+d, 2J (PtC) ) 226 Hz, CH2), 126.9-
1
CDCl3): δ 21.1 (s+d, J (PtP) ) 3505 Hz). 5a (L ) AsPh3, R )
Me): Yield: 234 mg, 84%. Anal. Calcd for C38H33As2ClOPt
(886.06): C 51.51; H 3.75; Cl 4.00. Found: C 51.48; H 3.83; Cl
1
4.22. IR (CsBr): ν(CO) 1650, ν(PtCl) 256 cm-1. H NMR (200
1
133.7 (phenyl-C), 202.9 (“t”+d, N ) 3 Hz, J (PtC) ) 951 Hz,
1
CO). 31P NMR (81 MHz, CDCl3): δ 7.3 (s+m, J (PtP) ) 3472
MHz, CDCl3): δ 1.33 (s br, 3H, CH3), 7.40 (m, 18H, m-, p-CH),
7.74 (m, 12H, o-CH). 13C NMR (50 MHz, CDCl3): δ 45.5 (s+d,
2J (PtC) ) 157 Hz, CH3), 128.8 (m-CH), 130.4 (p-CH), 131.9
3
2
Hz, J (PtP) ) 58 Hz, J (PP) ) 31/42 Hz).
Rea ction of [P t 2{(COMe)2H}2(µ-Cl)2] (1a ) w ith d p p e a t
Room Tem p er a tu r e. To a suspension of [Pt2{(COMe)2H}2-
(µ-Cl)2] (1a ) (100 mg, 0.16 mmol) in CD2Cl2 (4 mL) was added
bis(1,2-diphenylphosphino)ethane (127 mg, 0.32 mmol) at -30
°C, affording a pale yellow solution. The solution was slowly
warmed to ambient temperature for 30 min and investigated
by NMR spectroscopy (degree of conversion of 1a 100%; ratio
of [PtCl(COMe)(dppe)] (7):[PtCl2(dppe)] ca. 85-95:15-5 de-
tected by 31P NMR). To isolate 7 (in mixture with about 10%
[PtCl2(dppe)]), diethyl ether (10 mL) was added. After standing
overnight the off-white crystals were filtered off and dried
1
(i-C), 134.1 (o-CH), 214.9 (s+d, J (PtC) ) 844 Hz, CO). 5b (L
) AsPh3, R ) Et): Yield: 258 mg, 80%. Anal. Calcd for C39H35
-
As2ClOPt (900.09): C 52.04; H 3.92; Cl 3.93. Found: C 52.24;
1
H 4.08; Cl 4.29. IR (CsBr): ν(CO) 1656, ν(PtCl) 256 cm-1. H
NMR (200 MHz, CDCl3): δ -0.10 (t, 3H, CH3), 1.63 (t, 2H,
CH2), 7.40 (m, 18H, m-, p-CH), 7.72 (m, 12H, o-CH). 13C NMR
(50 MHz, CDCl3): δ 8.1 (s+d, 3J (PtC) ) 22 Hz, CH3), 52.6 (s+d,
2J (PtC) ) 150 Hz, CH2), 128.7 (m-CH), 130.3 (p-C), 132.1 (i-
1
C), 134.1 (o-CH), 215.9 (s+d, J (PtC) ) 854 Hz, CO).
Rea ction of [P t2{(COMe)2H}2(µ-Cl)2] (1a ) w ith P P h 3 in
a 1:2 Mola r Ra tio. To a suspension of [Pt2{(COMe)2H}2(µ-
Cl)2] (1a ) (100 mg, 0.16 mmol) in CDCl3 (5 mL) was added
triphenylphosphine (84 mg, 0.32 mmol) at room temperature.
NMR investigations of the resulting light green solution show
a degree of conversion of 1a of about 50% (1H NMR), formation
of [PtCl(COMe)(PPh3)2] (4a ) after 2 h, and quantitative forma-
tion of complexes [PtCl(Me)(CO)(PPh3)] (11a :11b ca. 7:3) after
2 days. 11a : 1H NMR (200 MHz, CDCl3): δ 1.24 (d+dd, 4.2H,
1
briefly in vacuo. IR (CsBr): ν(CO) 1633, ν(PtCl) 298 cm-1. H
NMR (200 MHz, CD2Cl2): δ 1.87 (d+dd, 3H, 4J (PH) ) 1.6 Hz,
3J (PtH) ) 14.2 Hz, CH3), 2.15 (m, 2H, CH2), 2.43 (m, 2H, CH2),
7.39 (m, 12H, m-, p-CH), 7.69-7.84 (m, 8H, o-CH). 13C NMR
(126 MHz, CDCl3): δ 24.3 (dd, 1J (PC) ) 25 Hz, 2J (PC) ) 7
Hz, CH2), 28.5 (dd, 1J (PC) ) 34 Hz, 2J (PC) ) 8 Hz, CH2), 41.9
(dd+d, 3J (PaC) ) 33 Hz, 3J (PbC) ) 4 Hz, 2J (PtC) ) 124 Hz,
CH3), 127.2-133.2 (phenyl-C), 244.3 (d, 1J (PC) ) 124 Hz, CO).
3
1
3J (PH) ) 7.6 Hz, J (PtH) ) 57 Hz, CH3), 7.32-7.78 (m, CH).
31P NMR (81 MHz, CDCl3): δ 30.6 (d+dd, J (PtP) ) 4439 Hz,
13C NMR (100 MHz, CDCl3): δ 2.7 (d+dd, 2J (PC) ) 87 Hz,
1J (PtC) ) 390 Hz, CH3), 128.2-135.0 (phenyl-C), 165.0 (d+dd,
2J (PC) ) 7 Hz, 1J (PtC) ) 1977 Hz, CO). 31P NMR (81 MHz,
2,3J (PaPb) ) 3 Hz), 32.2 (d+dd, J (PtP) ) 1407 Hz, 2,3J (PaPb)
1
) 3 Hz).
Rea ction of [P t 2{(COMe)2H}2(µ-Cl)2] (1a ) w ith d p p e a t
-30 °C. To a pale yellow suspension of [Pt2{(COMe)2H}2(µ-
Cl)2] (1a ) (100 mg, 0.16 mmol) in CD2Cl2 (3 mL) was added
bis(diphenylphosphino)ethane (127 mg, 0.32 mmol) at -30 °C,
affording a pale yellow solution of [Pt{(COMe)2H}(dppe)]Cl
(9a ) that was investigated by NMR spectroscopy at -30 °C
1
CDCl3): δ 25.2 (s+d, J (PtP) ) 1468 Hz). 11b: 1H NMR (200
3
3
MHz, CDCl3): δ 0.72 (d+dd, 1.8H, J (PH) ) 4.3 Hz, J (PtH)
) 55 Hz, CH3), 7.32-7.78 (m, CH). 13C NMR (100 MHz,
CDCl3): δ 8.7 (d+dd, 2J (PC) ) 5.5 Hz, 1J (PtC) ) 490 Hz, CH3),
128.2-135.0 (phenyl-C), 179.1 (d+dd, 2J (PC) ) 5.5 Hz,
1J (PtC) ) 958 Hz, CO). 31P NMR (81 MHz, CDCl3): δ 18.6
1
(degree of conversion of 1a 100%). H NMR (300 MHz, 243 K,
1
3
(s+d, J (PtP) ) 4093 Hz).
CD2Cl2): δ 2.02 (s+d, 6H, J (PtH) ) 16.5 Hz, CH3), 2.34 (“d”,
4H, N ) 17.0 Hz, CH2), 7.51 (m, 12H, m-, p-CH), 7.74 (m, 8H,
o-CH), 14.4 (s br, 1H, OHO). 13C NMR (75 MHz, 243 K, CD2-
Cl2): δ 27.7 (“sext”, N ) 49 Hz, CH2), 43.4 (“t”+d, N ) 21 Hz,
2J (PtC) ) 206 Hz, CH3), 129.2 (“t”, N ) 51 Hz, i-C), 129.3 (“t”,
N ) 10.1 Hz, m-CH), 131.8 (p-CH), 133.4 (“t”, N ) 11.8 Hz,
CH3). HMBC (500 MHz, 243 K, CD2Cl2): δ(1H)/(13C) ) 2.02/
265.3 (CH3, CO). 31P NMR (81 MHz, CD2Cl2): δ 39.5 (s+d,
1J (PtP) ) 1725 Hz).
Rea ction of [P t2{(COMe)2H}2(µ-Cl)2] (1a ) w ith [P tCl-
(COMe)(P P h 3)2] (4a ). To a suspension of [Pt2{(COMe)2H}2-
(µ-Cl)2] (1a ) (100 mg, 0.16 mmol) in CDCl3 (5 mL) was added
[PtCl(COMe)(PPh3)2] (4a ) (255 mg, 0.32 mmol) at ambient
temperature. After 2 days the resulting light green solution
was investigated by IR (ν(CO) 2107 (11b), 2077 (11a ), 1723
(MeCHO) cm-1) and NMR spectroscopy (1H NMR: quantita-
tive formation of [PtCl(Me)(CO)(PPh3)] (11), 11a :11b ca. 99:
1). The solvent was removed by evaporation, and the residue
(complex 12) was investigated by IR spectroscopy. IR (CsBr):
A solution of [Pt{(COMe)2H}(dppe)]Cl (9a ), prepared as
described above, was warmed to 0 °C for 10 min, and then