1108 Organometallics, Vol. 19, No. 6, 2000
Fornie´s et al.
) 14.4 Hz, CH2), 38.23 (s, Mecarbamate), 38.55 (s, Mecarbamate),
120-160 (m, C6H4) 175.66 (s, CO2), 176.51 (s, CO2), 205.16 (s,
CS2).
X ) F (4). This complex was prepared in a similar way to
3 with [Pd{CH2-C6H4-P(o-tolyl)2-κC,P}(S2CNMe2)] (B) (0.1537
g, 0.290 mmol) and Hg(O2CCF3)2 (0.1237 g, 0.290 mmol).
Yield: 0.1334 g, 59.72% (Found: C, 35.44; H, 2.80; N, 1.53.
Exp er im en ta l Section
Elemental analyses were determined using a Perkin-Elmer
240-B microanalyzer. IR spectra were recorded on a Perkin-
Elmer 599 spectrophotometer (Nujol mulls between polyeth-
ylene plates in the range 4000-200 cm-1). NMR spectra were
recorded on either a Varian XL-200 or a Varian Unity 300
NMR spectrometer using the standard references. [Pt{CH2-
C6H4-P(o-tolyl)2-κC,P}(S2CNMe2)] (A)6a and [Pd{CH2-C6H4-
P(o-tolyl)2-κC,P}(S2CNMe2)] (B)6b were prepared as described
elsewhere.
C
28F6H26HgNO4PPdS2 requires C, 35.16; H, 2.74; N, 1.46). IR
(ν/cm-1): 442m, 461m, 480s, 501m, 523m, 536m, 551w, 573m,
751s, 760s, 787s, 818s, 968m ν(C-S), 1567vs ν(C-N) (Me2-
NCS2-), 1143vs, 1168vs, 1189vs, 1676vs, 1709vs (CF3CO2-).
1H NMR (CD2Cl2, 188 K) δ: 1.47 (s, CH3 C∧P), 1.89 (s, CH3 C∧P),
[P t {CH 2-C6H 4-P (o-t olyl)2-KC,P }(S2CNMe2)(O2CCX3)-
Hg(O2CCX3)] [X ) H (1), F (2)]. X ) H (1). To a cooled
solution of [Pt{CH2-C6H4-P(o-tolyl)2-κC,P}(S2CNMe2)] (A)
(0.1950 g, 0.3151 mmol) in CHCl3 (25 mL) at -20 °C was added
Hg(O2CCH3)2 (0.1004 g, 0.3151 mmol). The solution, which
immediately acquired a bright yellow color, was stirred for 2
h at this temperature. It was then filtered through Celite and
evaporated to dryness. Addition of diethyl ether to the residue
at -20 °C afforded a yellow solid, 1 (0.2207 g, 74.7%) (Found:
C, 36.17; H, 3.49; N, 1.51. C28H32HgNO4PPtS2 requires C,
35.88; H, 3.44; N, 1.49). IR (ν/cm-1): 458m, 476m, 488m, 508w,
523m, 535m, 553m, 566m, 583m, 671m, 756s, 974m ν(C-S),
1538 ν(C-N) (Me2NCS2-), 1566m, 1576m (CH3CO2-). 1H NMR
(CDCl3, 223 K) δ: 1.91 (s, CH3 acetate), 1.97 (s, CH3 C∧P), 2.05
(s, CH3 C∧P), 2.11 (s, CH3 acetate), 2.96 (s, CH3 carbamate),
3.12 (s, CH3 carbamate), 3.90 (νA, 2J PtH ) 95.9 Hz, 2J HH ) 14.3
Hz, CH2), 4.34 (νB, 2J PtH ) 73.3 Hz, 2J HH ) 14.3 Hz, CH2), 6.49
2
3.05 (d, J HH ) 11.0 Hz, 1H, CH2), 3.12 (s, 6H, CH3 carbamate),
2
3.77 (d, J HH ) 11.0 Hz, 1H, CH2), 6.7-7.7 (m, 11H, C6H4),
3
3
8.87 (dd, H6, J PH ) 16.9 Hz, J H6H5 ) 6.1 Hz). 19F NMR δ:
-73.10 (s), -73.57 (s).
X-r a y Cr ysta l Str u ctu r e Deter m in a tion s of [P t {CH2-
C 6 H 4 -P (o-t o ly l)2 -KC,P }(S 2 C N Me 2 )(O 2 C C F 3 )H g (O 2 C -
CF3)].0.5Me2CO (2) an d [P d(S2CNMe2){µ-P (o-tolyl)2-C6H4-
CH2-}(µ-O2CMe)Hg(O2CMe)].H2O (3). Suitable crystals of
2‚0.5Me2CO were obtained by slow diffusion of n-pentane in
Me2CO/CH2Cl2 solutions of complex 2 at 5 °C. Suitable crystals
of 3‚H2O were obtained by slow diffusion of n-hexane in CH2-
Cl2 solutions of complex 3 at 5 °C.
Crystal data and other details of the structure analyses are
presented in Table 1. Crystals were fixed on top of glass or
quartz fibers and mounted on diffractometers. Unit cell
constants were determined from 60 accurately centered reflec-
tions with 25.9° < 2θ < 35.4° for 2‚0.5Me2CO and 60 reflections
in the range 24° < 2θ < 26° for 3‚H2O. Data were collected
using ω/θ scans for 2‚0.5Me2CO and ω scans for 3‚H2O. Three
check reflections were measured at regular intervals, and no
loss of intensity was observed in either case. The positions of
the heavy atoms were determined from the Patterson maps.
The remaining atoms were located in successive difference
Fourier syntheses. H atoms were added at calculated positions
(C-H ) 0.96 Å) with isotropic displacement parameters
assigned as 1.2 times the equivalent isotropic U’s of the
corresponding C atoms. For 2‚0.5Me2CO, there are two mol-
ecules of the platinum complex in the asymmetric part of the
unit cell. Three of the four CF3 groups of the trifluoroacetate
ligands are badly disordered. This disorder has been modeled
assigning two sets of positions for the fluorine atoms of each
CF3 group (0.5/0.5 occupancy). The thermal parameter of the
opposite fluorine atoms have been constrained to be the same.
The C-F distances have been restrained for all the CF3 groups.
The thermal parameters of the atoms of the acetone solvent
molecule have been constrained to be the same. The inter-
atomic distances in the solvent molecule have been restrained.
For 2‚0.5Me2CO a final difference electron density maps
showed one peak above 1 e Å-3 (1.37; largest diff hole -1.45)
lying 1.16 Å from the mercury atom. For 3‚H2O a final
difference electron density map showed no peaks above 1 e
Å-3 (max 0.69; largest diff hole -0.81). All calculations were
carried out using the program SHELXL-93.8
3
3
(dd, H6′, J PH ) 13.2 Hz, J H6′H ) 7.6 Hz), 7.0-7.5 (m, 10H,
5′
3
3
4
C6H4), 8.22 (ddd, H6, J PH ) 17.5 Hz, J H6H5 ) 7.7 Hz, J H6H4
) 1.8 Hz). 13C{1H} δ: 10.03 (s, CH2), 20.95 (d, J PC ) 7.1 Hz,
3
MeC∧P), 23.16 (s, Meacetate), 23.51 (d, 3J PC ) 3.1 Hz, MeC∧P), 24.31
(s, Meacetate), 37.45 (s, Mecarbamate), 39.83 (s, Mecarbamate), 120-
160 (m, C6H4) 176.80 (s, CO2), 177.29 (s, CO2), 205.58 (s, CS2).
X ) F (2). This complex was prepared in a similar way to
1 with [Pt{CH2-C6H4-P(o-tolyl)2-κC,P}(S2CNMe2)] (A) (0.2002
g, 0.3235 mmol) and Hg(O2CCH3)2 (0.138 g, 0.3235 mmol).
Yield: 0.2775 g, 82% (Found: C, 32.51; H, 2.55; N, 1.39.
C28F6H26HgNO4PPtS2 requires C, 32.17; H, 2.50; N, 1.34). IR
(ν/cm-1): 456m, 477m, 487m, 503w, 525m, 535m, 553m, 568m,
584m, 753m, 766m, 791s, 845s, 970m ν(C-S), 1556 ν(C-N)
(Me2NCS2-), 1151vs, 1192vs, 1667vs, 1684vs (CF3CO2-). 1H
NMR (CDCl3, 223 K) δ: 1.99 (s, CH3 C∧P), 2.01 (s, CH3 C∧P),
2
2.99 (s, CH3 carbamate), 3.19 (s, CH3 carbamate), 4.10 (νA, J PtH
)
102.5 Hz, 2J HH ) 14.2 Hz, CH2), 4.44 (νB, 2J PtH ) 78.0 Hz, 2J HH
3
3
) 14.2 Hz, CH2), 6.50 (dd, H6′, J PH ) 13.4 Hz, J H6′H ) 7.6
5′
3
Hz), 7.1-7.6 (m, 10H, C6H4), 8.06 (dd, H6, J PH ) 17.9 Hz,
3J H6H5 ) 7.3 Hz). 19F NMR δ: -73.38 (s), -74.16 (s). 13C{1H}
δ: 12.65 (s, CH2), 20.80 (s, MeC∧P), 23.46 (s, MeC∧P), 37.38 (s,
Mecarbamate), 39.89 (s, Mecarbamate), 110-160 (m, C6H4, CF3)
2
2
160.57 (q, J CF ) 36.22 Hz, CO2), 162.34 (q, J CF ) 36.22 Hz,
CO2), 203.81 (s, CS2).
[P d(S2CNMe2){µ-P (o-tolyl)2-C6H4-CH2-}(µ-O2CCX3) Hg-
(O2CCX3))] [X ) H (3), F (4)]. X ) H(3). To a solution of [Pd-
{CH2-C6H4-P(o-tolyl)2-κC,P}(S2CNMe2)] (B) (0.1500 g, 0.283
mmol) in CHCl3 (15 mL) was added Hg(O2CCH3)2 (0.090 g,
0.283 mmol), and the solution immediately acquired a yellow-
orange color. The mixture was stirred for 40 min until total
solution of the Hg(O2CCH3)2 and was then filtered through
Celite. Evaporation of the solvent to dryness and addition of
diethyl ether to the residue yielded 3 as a bright yellow solid
Resu lts
Rea ctivity of [M{CH2-C6H4-P (o-tolyl)2-KC,P }-
(S2CNMe2)] [M ) P t (A), P d (B)] w ith Mer cu r y(II)
Ca r boxyla tes. Syn th esis of Com p lexes 1-4. Com-
plexes [M(C∧P)(S2CNMe2)] [M ) Pt (A), Pd (B)] react
in chloroform with an equimolar amount of mercury-
(II) carboxylates, Hg(O2CR)2 (R ) CH3, CF3), to afford
complexes 1-4, as indicated in Scheme 1. All complexes
are obtained in good yield and are stable for a long time
in the solid state. However, in CHCl3 solution, only
(0.1890 g, 78.7%) (Found: C, 39.27; H, 3.92; N, 1.64. C28H32
-
HgNO4PPdS2 requires C, 39.63; H, 3.80; N, 1.65). IR (ν/cm-1):
444m, 463m, 480s, 495m, 523m, 537m, 550w, 571m, 756s, sh,
969m ν(C-S), 1564 ν(C-N) (Me2NCS2-), 1611m, 1626m
(CH3CO2-). 1H NMR (CD2Cl2, 253 K) δ: 1.37 (s, CH3 acetate),
1.57 (s, CH3 C∧P), 1.90 (s, CH3 C∧P), 2.01 (s, CH3 acetate), 2.98 (d,
2J HH ) 11.2 Hz, 1H, CH2), 3.15 (s, CH3 carbamate), 3.22 (s,
2
CH3 carbamate), 3.62 (d, J HH ) 11.2 Hz, 1H, CH2), 6.8-7.7 (m,
3
11H, C6H4), 9.06 (d, H6, J PH ) 16.5 Hz). 13C{1H} δ: 22.32 (s,
(8) Sheldrick, G. M. SHELXL-93, a program for crystal structure
determination; University of Go¨ttingen: Germany, 1993.
MeC∧P, acetate), 23.53 (s, MeC∧P), 23.77 (s, Meacetate), 31.64 (d, 3J PC