C. Pettinari et al. / Inorganic Chemistry Communications 10 (2007) 329–331
331
(0.180 g, 1.0 mmol) was added. The solution was stirred with warming
for 12 h and then cooled at 4 ꢀC. A pale-yellow crystalline precipitate
slowly formed, which was filtered off, washed with ethanol (5 mL),
dried under reduced pressure and shown to be compound 1 (0.307 g ,
yield 50%). M.p. 179–182 ꢀC. Anal. Calc. for C30H25AgN3O3P: C,
58.65; H, 4.10; N, 6.84%. Found: C, 58.53; H, 4.26; N, 6.64%. Km
(CH2Cl2, 10ꢁ3 M): 5.0 Xꢁ1 cm2 molꢁ1. Synthesis of PPh3AgNO2: bpy
(1:1) (2). Compound 2 (0.115 g, yield 20%) has been prepared
following a procedure similar to that reported for 1. M.p. 185–187 ꢀC.
Anal. Calc. for C28H23AgN3O2P: C, 58.76; H 4.05; N, 7.34. Found: C,
values for the signal at ca. 11 ppm is 443 Hz, representative
of an AgP2O2 coordination environment and suggesting a
dissociation-equilibrium as that in Eq. (3).
2½AgðphenÞðPPh3ÞðNO2Þꢀ ꢀ ½AgðPPh3Þ2ðNO2Þꢀ
þ ½AgðphenÞ2ðNO2Þꢀ
ð3Þ
The results of the single crystal X-ray study for 3 [12] are
consistent with the description of the array as of 1:1:1
AgNO2: PR3: dmp stoichiometry and connectivity, all
components being closely associated as a single aggregate,
one of which, devoid of crystallographic symmetry, com-
prises the asymmetric unit of the structure. As with the
nitrate analogue, the core of the molecule comprises the
tightly bound PPh3 and N,N0-dmp components, the
PAgN2 array comprising a quasi-trigonal planar array. In
the counterpart nitrate structure [2] (which contains two
independent molecules in the asymmetric unit), the planar-
ity of each array is perturbed by the approach of semi-
bidentate nitrate groups Ag–O(,O0) being 2.678(3)
58.45; H, 4.12; N, 7.23%. Km (CH2Cl2, 10ꢁ3 M): 1.0 Xꢁ1 cm2 molꢁ1
.
Synthesis of PPh3AgNO2: dmp (1:1) (3). To a benzene solution
containing PPh3AgNO2 [5] (0.417 g, 1.0 mmol), dmp (0.417 g,
2.0 mmol) was added. The solution was stirred under reflux for 12 h
and then cooled at 4 ꢀC.A colourless crystalline precipitate slowly
formed, which was filtered off, washed with benzene (5 mL), dried
under reduced pressure and shown to be compound 3 (0.312 g , yield
50%). Recrystallised from hot-benzene. M.p. > 200 ꢀC dec. Anal.
Calc. for C32H27AgN3O2P: C, 61.55; H, 4.36; N, 6.73%. Found: C,
61.23; H, 4.41; N, 6.54%. Km (CH2Cl2, 10ꢁ3 M): 28.4 Xꢁ1 cm2 molꢁ1
.
[7] (PPh3)2AgNO2: Him (1:1) (4). Compound 4 (0.373 g, yield 50%) has
been prepared following a procedure similar to that reported for 1, by
using [(PPh3)2AgNO2] and Him. M.p. 178 ꢀC dec. Anal. Calc. for
C39H34AgN3O2P2: C, 62.75; H, 4.59; N, 5.63; O. Found: C, 62.62; H,
4.71; N, 5.48%. IR (nujol, cmꢁ1): 3100w (NH) 1583w, 1538w, 1437sh,
1331m, 1305m, 1199w, 823m, 516, 494s, 433s, 280m, 247w. 1H NMR
˚
(3.008(3)) (mol. 1), 2.721(5) (3.012(6) A) (mol. 2); the
PAgN2 angle sums are 354.6, 353.5ꢀ. Here, the nitrite
approaches as a symmetrical bidentate ligand, bound much
more strongly, the PAgN2 angle sum being reduced to
(CDCl3, 293 K): d, 6.99 (s, 1H, CHHim), 7.2–7.8m (32H, PC18H15
+
CHHim). Km (CH2Cl2, 10ꢁ3 M): 0.5 Xꢁ1 cm2 molꢁ1. (PPh3)AgNO2:
Him (1:1) (5). Compound 5 (0.373 g, yield 50%) has been prepared
following a procedure similar to that reported for 1, by using
[(PPh3)AgNO2] and Him. M.p. 138–141ꢀC dec. Anal. Calc. for
C21H19AgN3O2P: C, 52.09; H, 3.95; N, 8.68. Found: C, 52.12; H,
3.91; N, 8.47%. IR (nujol, cmꢁ1): 3100w (NH) 1583w, 1535w, 1435sh,
1326m, 1237m, 849w, 825m, 511m, 503m, 493s, 433, 420w, 249w, 201w.
1H NMR (CDCl3, 293 K): d, 7.0(s, 1H, CHHim), 7.2–7.5; 7.6–7.8m
0
˚
324.7ꢀ and Ag–O,O much shorter (2.512(4), 2.543(5) A).
In compensation, in the nitrate, Ag–N (2.313(4) –
˚
2.355(3), Ææ 2.34(2) A) are shorter than in the present
˚
˚
(2.392(4), 2.364(3) A); Ag–P (2.382(1) A (·2)) are essen-
tially identical. The disposition of the PPh3 ligand appears
to be influenced by the steric effect of the methyl groups,
phenyl rings 1,3 straddling CH3(261), while ring 2, con-
fronting the approach of C(161) lies quasi-normal to that
approach, seemingly without other substantial interaction
since the pair of P–Ag–N angles are essentially identical
(126.72(8), 127.19(9)ꢀ), although the two Ag–N distances
(17H, PC18H15 + CHHim). Km (CH2Cl2, 10ꢁ3 M): 0.2 Xꢁ1 cm2 molꢁ1
.
[8] C. Pettinari, manuscript in preparation.
[9] 1 Æ H2O: IR (nujol, cmꢁ1): 3450br (OH) 3150w (CH), 1304w, 1221br
(NO2) 1153w, 1093w, 1026w, 995w, 969br; 840m (ONO) 742m, 725s,
1
694m, 512m, 500m, 438br. H NMR (CDCl3, 293 K): d, 1.58 (s, 2H;
H2O), 7.2–7.4m (15H, PC18H15), 7.45–7.68m, 7.86s, 8.30–8.35m,
9.11–9.13m (8H, CHphen). 31P NMR (CDCl3, 298 K): d, 10.9 br. 2: IR
(nujol, cmꢁ1): 3160w (CH), 1305w, (NO2) 1159br, 1093w, 995vw,
965br; 850w (ONO), 820w, 763sh, 722m, 694m, 667w, 649w, 638w,
˚
differ by ca. 0.03 A in the manner expected.
Appendix A. Supplementary data
1
619w; 518m, 506m, 491m (PPh3) 437w, 419w, 412w, 395w. H NMR
(CDCl3, 293 K): d, 7.3–7.5m (15H, PC18H15), 7.63–7.70m, 7.82–
7.91m, 8.43–8.47m, 8.71–8.73m (8H, CHbpy). 31P NMR (CDCl3,
Supplementary data associated with this article can be
298 K): d, 13.8 br.31
(1J(31P-109Ag):
450 Hz;
P
NMR (CDCl3, 223 K): d, 11.7 dd
1J(31P-107Ag):
390 Hz), 18.9 dd
(1J(31P-109Ag): 741 Hz; 1J(31P-107Ag): 641 Hz). 3: IR (nujol, cmꢁ1):
1616m, 1592m, 1551m, 1496s, 1430m, 1350m, 1204s (NO2) 886w,
860s, 840w, 824w, 816w (ONO) 552s, 512m, 500m, 478s, 439m, 430s,
419m, 396w, 311w, 280w, 246w, 228w, 213w. 1H NMR (CDCl3,
293 K): d, 2.87s (s, 6H CH3dmp), 7.29–7.52m (15H, PC18H15), 7.70br,
8.14br, 8.18br (6H, CHdmp). 31P NMR (CDCl3, 298 K): d, 9.1 br.
[10] K. Shobatake, C. Postmus, J.F. Ferraro, K. Nakamoto, Appl.
Spectrosc. 23 (1969) 12.
References
[1] C. di Nicola, Effendy, F. Marchetti, C. Pettinari, B.W. Skelton, A.H.
[2] Effendy, F. Marchetti, C. Pettinari, B.W. Skelton, A.H. White, Inorg.
[3] Effendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, A.H.
[11] J. Bradbury, K.P. Forest, R.H. Nuttall, D.W.A. Sharp, Spectrochim.
Acta 23 (1967) 2701.
[12] AgNO2: PPh3: dmp (1:1:1), 3. C32H27AgN3O2P, M = 624.4. Mono-
clinic, space group C2/c ðC62h; No:15Þ, a = 23.887(7), b = 9.775(3), c =
3
ꢁ3
.
˚
˚
25.126(17) A, b = 98.45(5)ꢀ, V = 5803 A . Dc (Z = 8) = 1.429 g cm
l
[4] A. Cingolani, Effendy, M. Pellei, C. Pettinari, C. Santini, B.W.
Skelton, A.H. White, Inorg. Chem. 41 (2002) 6633.
Mo = 0.78 mmꢁ1; specimen: 0.28 · 0.26 · 0.65 mm; Aꢂmin = max (gauss-
ian correction) = 1.16, 1.26. 2hmax = 50ꢀ; monochromatic Mo Ka
radiation, k = 0.71073 A; single counter instrument, 2h/h scan mode;
T ca. 295 K. 10084 total reflections (hemisphere) merging to 5109
unique (Rint = 0.042), 3795 (I > 3r (I)) ‘observed’; R = 0.043,
Rw = 0.052 (weights: r2(F) + 0.0004(F2)ꢁ1). CCDC 609969.
[5] Effendy, J.V. Hanna, F. Marchetti, D. Martini, C. Pettinari, R.
Pettinari, B.W. Skelton, A.H. White, Inorg. Chim. Acta 359 (2004)
1523.
[6] Synthesis of PPh3AgNO2: phen (1:1). H2O (1 Æ H2O). To an ethanol
solution containing PPh3AgNO2 [5] (0.417 g, 1.0 mmol), phen
˚