D. Moigno et al. / Inorganica Chimica Acta 334 (2002) 355Á
/364
363
integrated FRA 106 Raman module (resolutionꢀ
/
3
2.76 (m, 12H, PCHCH3), 1.35 [dvt, Nꢀ
J(HH)ꢀ
50.3 MHz): d 163.1 [dt, J(RhC)ꢀ
Hz, RhCN), 132.8 (s, ipso-C of C6H4), 131.4, 122.3,
120.4 (all s, C6H4), 26.3 (vt, Nꢀ10.2 Hz, PCHCH3),
20.6 (s, PCHCH3). 31P NMR (CD2Cl2, 81.0 MHz): d
45.5 [d, J(RhP)ꢀ122.1 Hz]. UV (hexane): lmax 298, 340
nm.
/
13.5 Hz,
cmꢂ1) at r.t. Radiation of 1064 nm from a NdÁ
/YAG
/
6.9 Hz, 72H, PCHCH3]. 13C NMR (CD2Cl2,
laser was employed for excitation of crystalline samples
contained in NMR tubes under argon. Melting points
(m.p.) were determined by DTA. The mass spectrum of
2 was measured on a Finnigan 90 MAT instrument.
/
75.4 Hz, J(PC)ꢀ15.9
/
/
UVÁ
nm in hexane using a PerkinÁ
spectrometer Lambda 19. The extinction coefficients o
are given in Mꢂ1 cmꢂ1
/
Vis spectra were recorded in the range of 300Á
/
700
/
/
Elmer, UVÁVIDÁNIR
/
/
.
4.3. Crystal structure analysis of 2
4.1. Preparation of trans-[{RhCl(PiPr3)2}2{m-1,3-
(CN)2C6H4}] (2)
Single crystals were grown by slow diffusion of
pentane into a saturated solution of 2 in CH2Cl2 at
0 8C. Crystal structure determination of 2:
A solution of 511 mg (0.72 mmol) of 4 in 5 ml of
benzene was treated first with 550 ml (2.88 mmol) of
PiPr3 and then dropwise with a solution of 71.4 mg (0.72
mmol) 1,3-(CN)2C6H4 in 25 ml of ether. During the
addition of the diisocyanide a change of color from
purple to yellow occurred. After the reaction mixture
was stirred for 12 h at r.t., the solvent was removed in
vacuo. The residue was extracted twice with 20-ml
portions of ether, the combined extracts were filtered
and the filtrate was evaporated to dryness in vacuo. The
resulting yellow solid was washed twice with 3-ml
portions of pentane and dried; yield 432 mg (75%),
m.p. (decomposition) 112 8C. Anal. Found: C, 50.40;
H, 8.30; N, 2.63. Calc. for C44H88Cl2N2P4Rh2: C, 50.53;
H, 8.48; N, 2.67%. MS FAB: m/z 1044 (1.5, Mꢁ);
matrix: 2-nitrophenyloctylether. 1H NMR (CD2Cl2, 200
C44H88Cl2N2P4Rh2, Mrꢀ
/
1045.76; monoclinic, space
4, aꢀ18.586(4), bꢀ
104.72(3)8, Vꢀ
1.328 g cmꢂ3, F(000) 2200, lꢀ
173(2) K, m(Mo Ka)ꢀ
0.886 mmꢂ1
Crystal size 0.3ꢃ0.3ꢃ u 548.088;
0.3 mm3; 3.565
18 637 reflections were measured, 3976 of these were
independent (Rint 0.0523) and employed in the struc-
ture refinement (266 parameters). The R values are
R1ꢀ jFcjj)/(SjFoj)ꢀ0.0369 [I ꢀ2s(I)] and
(SjjFojꢂ
wR2ꢀ 0.0887 (all
group C2/c (no. 15), Zꢀ
/
/
/
˚
12.289(3), cꢀ
5228.6(18) A , Dcalc
/
23.669(5) A, bꢀ
/
/
3
˚
ꢀ
/
/
˚
0.71073 A, Tꢀ
/
/
.
/
/
/
/
ꢀ
/
/
/
/
/
Fc ) ])/(S[wFo ])}1/2ꢀ
/
2
2 2
4
/
{(S[w(Fo ꢂ
/
data); min./max. residual electron density, 0.793/ꢂ
/
0.830 e Aꢂ3. Data were collected on a IPDS (STOE)
˚
diffractometer. A semi-empirical absorption correction
was applied. The structure was solved by direct methods
MHz): d 7.20Á
PCHCH3), 1.35 [dvt, Nꢀ
72H, PCHCH3]. 13C NMR (CD2Cl2, 50.3 MHz): d
166.4 [dt, J(RhC)ꢀ72.6 Hz, J(PC)ꢀ16.5 Hz, RhCN],
133.2 (s, ipso-C of C6H4), 130.9, 121.6, 120.2 (all s,
C6H4), 24.3 [vt, Nꢀ10.1 Hz, PCHCH3], 20.1 (s,
PCHCH3). 31P NMR (CD2Cl2, 81.0 MHz): d 47.6 [d,
J(RhP)ꢀ127.2 Hz]. UV (hexane): lmax 331 (oꢀ27 860),
430 (oꢀ6760) nm.
/
6.70 (m, 4H, C6H4), 2.57 (m, 12H,
(
(
SHELXS-97) [21] and refined against F2 by least-squares
SHELXL-97) [22]. All non-hydrogen atoms were refined
/
13.5 Hz, J(HH)ꢀ6.6 Hz,
/
anisotropically. The isopropyl group with C26, C27 and
C28 was found disordered (ratio 55:45) and the posi-
tions of these carbon atoms refined with restraints.
/
/
/
/
/
4.4. Computational details
/
DFT calculations were performed using GAUSSIAN 98
[23] and Becke’s 1988 exchange functional [24] in
4.2. Preparation of trans-[{RhI(PiPr3)2}2{m-1,3-
(CN)2C6H4}] (3)
combination with the PerdewÁ
rected correlation functional (BPW91) [25]. For the
model compounds trans-[RhX(CNC6H5)(PMe3)2] (Xꢀ
/Wang 91 gradient-cor-
A solution 105 mg (0.10 mmol) of 2 in 8 ml of acetone
was treated with 90 mg (0.6 mmol) of NaI and stirred
for 5 h at r.t. A change of color from yellow to orange
occurred. The solvent was evaporated in vacuo, and the
residue was extracted twice with 15-ml portions of
CH2Cl2. The combined extracts were filtered and the
filtrate was brought to dryness in vacuo. The resulting
orange solid was washed twice with 2-ml portions of
pentane and dried; yield 121 mg (98%), m.p. (decom-
position) 117 8C. Anal. Found: C, 42.75; H, 6.98; N,
2.61. Calc. for C44H88I2N2P4Rh2: C, 43.00; H, 7.22; N,
/
F, Cl) and trans-[{RhF(PMe3)2}2{m-1,3-(CN)2C6H4}]
the Los Alamos effective core potential plus double
zeta (LANL2DZ) [26,27] was employed for rhodium,
whereas the DunningÁ
set with or without polarization and diffuse function
(D95, D95ꢁ(d)) was used for the other atoms [28]. The
/Huzinaga full double zeta basis
/
following notation has been used for the computational
methods used. DFT1: BPW91/LANL2DZ for all atoms;
DFT2: BPW91/LANL2DZ for Rh and D95ꢁ(d) for the
/
other atoms. In case of 1, the geometry, the normal
modes and the Raman intensities were calculated using
2.28%. IR (KBr): n(CÅ
/
N) 2035 (vs), 2001 (vs) cmꢂ1. 1H
6.80 (m, 4H, C6H4),
NMR (CD2Cl2, 200 MHz): d 7.25Á
/
the Pople basis set 6-31ꢁ
/
G(d) [29Á31].
/
Moigno, Damien
