G. van Koten et al.
FULL PAPER
2
], 40.6 16.2 Hz, 1 H, trans CH=CH], 6.95 [d, 3J(H,H) = 16.2 Hz, 1 H,
7
7.9 [ J(C,Pt) = 66.5 Hz; CH
2
N], 54.6 [CH
2
N(CH
3
)
2
195
1
3
[ArN(CH
3
)
2
] ppm.
Pt{ H} NMR (64 MHz, CD
2
Cl
2
): δ =
trans CH=CH], 6.99 (s, 2 H, ArH), 4.04 [s, J(H,Pt) = 45.1 Hz, 4
3
13
1
–
1
9
5
4
3173 ppm. IR (ATR): ν˜ = 3009, 2978, 2916, 2797, 1604, 1520,
448, 1351, 1271, 1217, 1187, 1167, 1157, 1127, 1084, 1060, 1041,
H, CH
NMR (75 MHz, CD
138.0, 132.7, 131.2, 128.2, 124.6, 118.0 (Cmeta to Pt), 92.1, 77.9
2
], 3.05 [s, J(H,Pt) = 37.4 Hz, 12 H, CH
3
] ppm. C{ H}
2
Cl ): δ = 147.5 (Cipso to Pt), 144.4, 138.1,
2
–
1
44, 880, 835, 808, 706 cm . MS (ES+, CH
3
CN/CH
Pt (566.18): calcd. C (CH
6.60, H 5.33, N 7.41; found C 46.68, H 5.31, N 7.36. δ = –3149 ppm. IR (ATR): ν˜ = 3002, 2972, 2920, 1622, 1586, 1575,
2 2
Cl ): m/z =
+
+
195
1
66.17 [M] , 531.19 [M – Cl] . C22
H30ClN
3
2 3 2 2 2
N), 54.6 [N(CH ) ] ppm. Pt{ H} NMR (64 MHz, CD Cl ):
1
7
483, 1450, 1430, 1398, 1334, 1183, 1085, 1001, 967, 833, 806, 730,
[
2 2 6 4
PtCl{NCN(C H C H -OMe-4Ј)-4}] (2): Diethyl 4-methoxyben-
–
1
+
11 cm . MS (ES+, CH
3
CN/CH
Pt (649.86): calcd. C 36.96, H 3.72, N 4.31;
found C 37.04, H 3.78, N 4.28.
2 2
Cl ): m/z = 649.06 [M] , 614.10
zylphosphonate (8b; 126 mg, 0.488 mmol), 9 (200 mg, 0.445 mmol).
+
[M – Cl] . C20H24ClIN
2
Product isolated as a yellow powder (132 mg, 0.238 mmol, 53%).
1
3
H NMR (300 MHz, CD
2
Cl
2
): δ = 7.43 [d, J(H,H) = 8.8 Hz, 2 H,
3
ArH], 7.00 [d, J(H,H) = 16.2 Hz, 1 H, trans CH=CH], 6.97 (s, 2
H, ArH), 6.88 [d, J(H,H) = 8.8 Hz, 2 H, ArH], 6.87 [d, J(H,H)
[PtCl{NCN(C -CN-4Ј)-4}] (6): Diethyl 4-cyanobenzylphos-
2 2 6 4
H C H
3
3
phonate (8f; 155 mg, 0.612 mmol), 9 (250 mg, 0.556 mmol). Prod-
uct isolated as a yellow powder (275 mg, 0.501 mmol, 90%).
NMR (300 MHz, CD
ArH], 7.39 [d, J(H,H) = 8.3 Hz, 2 H, ArH], 7.15 [d, J(H,H) =
3
=
CH
16.2 Hz, 1 H, trans CH=CH], 4.08 [s, J(H,Pt) = 45.9 Hz, 4 H,
1
H
3
2
], 3.81 (s, 3 H, OCH
3
), 3.05 [s, J(H,Pt) = 37.0 Hz, 12 H, CH
Cl ): δ = 159.4 (ArCOMe),
46.7 (Cipso to Pt), 144.2, 133.4, 131.0, 128.1, 127.5, 125.4, 117.6
3
]
Cl
2
): δ = 7.61 [d, J(H,H) = 8.5 Hz, 2 H,
3
2
ppm. 13C{ H} NMR (75 MHz, CD
1
3
3
2
2
1
3
16.5 Hz, 1 H, trans CH=CH], 7.04 [d, J(H,H) = 16.5 Hz, 1 H,
3
2
[
J(C,Pt) = 36.0 Hz; Cmeta to Pt], 114.4, 77.9 [ J(C,Pt) = 62.1 Hz;
3
trans CH=CH], 7.02 (s, 2 H, ArH), 4.05 [s, J(H,Pt) = 45.6 Hz, 4
195
1
CH
(
2
1
CH
C
4
2
N], 55.6 (OCH
Cl ): δ = –3164 ppm. IR (ATR): ν˜ = 3003, 2973,
921, 2838, 1625, 1604, 1572, 1509, 1451, 1297, 1252, 1174, 1109,
3
), 54.5 [N(CH
3
)
2
] ppm.
Pt{ H} NMR
3
13
1
H, CH
2
], 3.05 [s, J(H,Pt) = 37.7 Hz, 12 H, CH
Cl ): δ = 148.6 (Cipso to Pt), 144.5, 142.9,
34.0, 132.8, 132.1, 126.7, 123.8, 119.5 (CN), 118.3 [ J(C,Pt) =
3
] ppm. C{ H}
64 MHz, CD
2
2
NMR (75 MHz, CD
1
3
2
2
3
–1
083, 1029, 965, 881, 855, 833, 808, 734, 722, 705 cm . MS (ES+,
2
7.1 Hz; Cmeta to Pt], 110.2, 77.8 [ J(C,Pt) = 64.3 Hz, CH
2
N], 54.5
): δ =
+
+
3
CN): m/z = 559.19 [M – Cl + CH
27ClN OPt (553.99): calcd. C 45.53, H 4.91, N 5.06; found C
5.46, H 4.87, N 4.88.
3
CN] , 518.12 [M – Cl] .
[N(CH
)
2
]
ppm.
195
Pt{ H} NMR (64 MHz, CD
1
Cl
3
2
2
21
H
2
–3138 ppm. IR (ATR): ν˜ = 2972, 2919, 2223 (CN), 1664, 1626,
1
8
CH
599, 1579, 1505, 1450, 1333, 1172, 1084, 1016, 955, 882, 864, 833,
–
1
18, 725, 707 cm . MS (ES+, CH
3
CN): m/z = 554.19 [M – Cl +
24ClN Pt (548.97): calcd. C
[PtCl{NCN(C
2
H
2
C
6
H
4
-SiMe
3
-4Ј)-4}] (3): Diethyl 4-trimethylsilyl-
(200 mg,
.445 mmol). Product isolated as a pale white powder (230 mg,
+
+
3
CN] , 513.16 [M – Cl] . C21
H
3
benzylphosphonate (8c; 146 mg, 0.486 mmol),
0
9
45.95, H 4.41, N 7.65; found C 46.08, H 4.51, N 7.54.
0
.386 mmol, 87%). 1H NMR (300 MHz, CD
2 2
Cl ): δ = 7.50 [d,
[PtCl{NCN(C -NO -4Ј)-4}] (7): Diethyl 4-nitrobenzylphos-
2
H
2
C
6
H
4
2
3
J(H,H) = 8.3 Hz, 2 H, ArH], 7.47 [d, 3J(H,H) = 8.3 Hz, 2 H,
phonate (8g; 122 mg, 0.447 mmol), 9 (182 mg, 0.405 mmol). Prod-
uct isolated as a brown–red powder (166 mg, 0.292 mmol, 72%).
3
ArH], 7.05 (s, 2 H, ArH), 7.01 (s, 2 H, CH=CH), 4.04 [s, J(H,Pt)
3
=
45.7 Hz, 4 H, CH
.272 [s, 9 H, Si(CH
δ = 147.1 (Cipso to Pt), 144.4, 139.8, 138.7, 134.1, 133.1, 130.5,
2
], 3.05 [s, J(H,Pt) = 37.4 Hz, 12 H, CH
3
],
):
1
3
H NMR (300 MHz, CD
2
Cl
2
): δ = 8.18 [d, J(H,H) = 8.8 Hz, 2 H,
] ppm. 13C{ H} NMR (75 MHz, CD
1
Cl
0
3
)
3
2
2
3
3
ArH], 7.62 [d, J(H,H) = 8.8 Hz, 2 H, ArH], 7.21 [d, J(H,H) =
3
16.4 Hz, 1 H, trans CH=CH], 7.10 [d, J(H,H) = 16.4 Hz, 1 H,
3
2
1
=
25.9, 125.7, 118.0 [ J(C,Pt) = 34.9 Hz; Cmeta to Pt], 77.9 [ J(C,Pt)
3
trans CH=CH], 7.05 (s, 2 H, ArH), 4.06 [s, J(H,Pt) = 46.7 Hz, 4
1
95
1
64.3 Hz; CH
2
N], 54.6 [N(CH
Cl ): δ = –3160 ppm. IR (ATR): ν˜ = 3013,
953, 1625, 1581, 1451, 1396, 1335, 1298, 1248, 1111, 1084, 1015,
64, 832, 804, 755, 719, 691, 670 cm . MS (ES+, CH
96.21 [M + H] , 560.22 [M – Cl] . C23
3
)
2
], –1.1 [Si(CH
3
)
3
] ppm. Pt{ H}
3
13
1
H, CH
2
], 3.06 [s, J(H,Pt) = 37.4 Hz, 12 H, CH
Cl ): δ = 149.1 (Cipso to Pt), 146.6, 145.1,
44.6, 135.1, 132.0, 126.7, 124.5, 123.4, 118.5 [ J(C,Pt) = 34.9 Hz;
3
] ppm. C{ H}
NMR (64 MHz, CD
2
2
NMR (75 MHz, CD
1
2
2
2
9
5
3
–
1
2
Cl
2
): m/z =
PtSi (596.14):
2
C
meta to Pt], 77.8 [ J(C,Pt) = 63.2 Hz; CH
2
N], 54.6 [N(CH
): δ = –3133 ppm. IR (ATR):
ν˜ = 2978, 2917, 1624, 1592, 1573, 1506, 1450, 1333, 1312, 1180,
3 2
) ] ppm.
+
+
H33ClN
2
195
1
2 2
Pt{ H} NMR (64 MHz, CD Cl
calcd. C 46.34, H 5.58, N 4.70; found C 46.28, H 5.64, N 4.73.
PtCl{NCN(C )-4}] (4): Diethyl benzylphosphonate (8d;
1 mg, 0.267 mmol), 9 (100 mg, 0.222 mmol). Product isolated as a
–
1
1107, 1086, 1020, 955, 910, 859, 839, 749, 711, 691 cm . MS (ES+,
[
6
2 2 6 5
H C H
+
+
3 3
CH CN): m/z = 574.15 [M – Cl + CH CN] , 533.15 [M – Cl] .
C H ClN O Pt (568.96): calcd. C 42.22, H 4.25, N 7.39; found
20 24 3 2
C 42.08, H 4.20, N 7.28.
1
pale white powder (92 mg, 0.176 mmol, 79%). H NMR (300 MHz,
CD Cl ): δ = 7.49 [d, J(H,H) = 7.1 Hz, 2 H, ArH], 7.33 [t, J(H,H)
2 2
=
[
3
3
3
7.1 Hz, 2 H, ArH], 7.23 [t, J(H,H) = 7.1 Hz, 1 H, ArH], 7.06
X-ray Crystal Structure Determinations: X-ray intensities were mea-
sured with a Nonius KappaCCD diffractometer with rotating an-
ode and graphite monochromator (λ = 0.71073 Å) at a temperature
of 150 K. The structures were solved with automated Patterson
d, 3J(H,H) = 15.9 Hz, 1 H, trans CH=CH], 7.01 [d, 3J(H,H) =
3
1
5.9 Hz, 1 H, trans CH=CH], 7.00 (s, 2 H, ArH), 4.04 [s, J(H,Pt)
3
=
45.9 Hz, 4 H, CH
2
], 3.05 [s, J(H,Pt) = 37.9 Hz, 12 H, CH
C{ H} NMR (75 MHz, CD Cl ): δ = 147.0 (Cipso to Pt), 144.4,
38.3, 133.1, 130.3, 129.0, 127.4, 126.4, 125.8, 117.9 (Cmeta to Pt),
3
] ppm.
1
3
1
2
2
methods[ and refined with SHELXL-97
94]
[95]
2
against F of all re-
1
7
CD
flections. The initial atomic coordinates of 2 were taken from iso-
structural compound 6. Geometry calculations and checking for
higher symmetry were performed with the PLATON[ program.
2 3 2
N), 54.6 [N(CH )
] ppm. 1 Pt{ H} NMR (64 MHz,
95
1
7.9 (CH
Cl ): δ = –3158 ppm. IR (ATR): ν˜ = 3018, 2973, 2920, 1625,
581, 1496, 1450, 1334, 1300, 1085, 964, 831, 753, 708, 692 cm .
2
2
96]
–
1
1
2 2
In structure 1, the CH Cl solvent molecule was refined with a
+
MS (ES+, CH
3
CN/CH
88.12 [M – Cl] . C20
2
Cl
25ClN
N 5.35; found C 45.76, H 4.88, N 5.23.
2
): m/z = 529.18 [M – Cl + CH
3
CN] ,
partial occupation. One of the metal complexes was disordered
about the central double bond. In 1 and 7, hydrogen atoms were
introduced in geometrically optimized positions and refined with a
riding model. In 2, 5 and 6, all hydrogen atoms were located in the
difference Fourier map and refined with a riding model. Further
crystallographic details are given in Table 7. CCDC-626890 (com-
pound 1), -626891 (compound 2), -626892 (compound 5), -626893
(compound 6) and -626894 (compound 7) contain the supplemen-
+
4
H
2
Pt (523.96): calcd. C 45.85, H 4.81,
[PtCl{NCN(C -I-4Ј)-4}] (5): Diethyl 4-iodobenzylphos-
2 2 6 4
H C H
phonate (8e; 86 mg, 0.243 mmol), 9 (100 mg, 0.222 mmol). Product
isolated as a light yellow powder (123 mg, 0.189 mmol, 85%). H
NMR (300 MHz, CD
ArH], 7.25 [d, J(H,H) = 8.2 Hz, 2 H, ArH], 7.04 [d, J(H,H) =
1
Cl
2
): δ = 7.66 [d, 3J(H,H) = 8.2 Hz, 2 H,
2
3
3
1432
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 1422–1435