19F δ Ϫ8.1 (br s, 2F, BF2 trans to CO) and Ϫ10.0 (br s, 4F, BF2
were solved and refined against F2 using SHELXL 97.35 In
1
trans to PPh3); 13C-{1H} δ 135.2 (d, ipso-C of PPh3, JPC = 46),
compound 3 positional disorder was identified between the
carbonyl ligand and the BF2 group trans to it. Each unit was
refined anisotropically over two sites in a ratio of 67:33(5).
In 4 disorder was observed between one of the NO2 groups
and residual chloride and was modelled in a 66:34(2) ratio with
the chloride refined isotropically. Constraints were applied to
the refinement of the NO2 group so that the adps mirrored those
of the neighbouring NO2 ligand. In [Co(PMe3)4][BF4] the anion
was disordered over a 3-fold rotation axis and modelled with
two separate images [73:27(2) ratio] with F(2) having two
different positions. Hydrogen atoms were included in idealised
positions.
2
134.1 (d, o-C of PPh3, JPC = 12), 131.1 (s, p-C of PPh3) and
3
1
128.9 (d, m-C of PPh3, JPC = 10 Hz); H δ 7.39 (m, 8H, PPh3)
and 7.29 (m, 22H, PPh3). C37H30B3F6IrOP2 requires C, 49.85;
H, 3.40. Found C, 49.70; H, 3.00%. IR (KBr disk): ν(CO)
2039 cmϪ1.
cis-[Pt(NO2)2(dppb)] 4. A solution of dppb (0.103 g, 0.242
mmol) in ethanol (30 cm3) and thf (6 cm3) was transferred to a
pressure equalising dropping funnel fitted above a Schlenk flask
containing a yellow-green solution of K2[Pt(NO2)4] (0.110 g,
0.241 mmol) in water (10 cm3). Dropwise addition of the dppb
solution to the stirred aqueous solution of the nitritoplatinate
salt at room temperature resulted in the immediate formation
of a white precipitate. After stirring for 16 h the white solid was
collected by vacuum filtration (in air), washed with distilled
water (4 × 10 cm3), ethanol (3 × 10 cm3) and Et2O (2 × 10 cm3)
and then dried by vacuum affording complex 4 as a white
microcrystalline solid (0.084 g, 49%). NMR data (d6-dmso):
Crystal data for cis-[Pt(BF2)2(dppb)] 2. M = 719.15, triclinic,
¯
space group P1 (no. 2), a = 8.924(4), b = 11.185(7), c =
14.678(12) Å, α = 85.61(6), β = 80.07(5), γ = 71.32(4)Њ, U =
1366.7(15) Å3, T = 173(2) K, Z = 2, µ(Mo-Kα) = 5.29 mmϪ1,
14332 reflections measured, 6163 unique (Rint = 0.044), final
R1 = 0.034 [5100 data, I > 2σ(I)].
1
31P-{1H} δ Ϫ3.1 (t, JPtP = 3026 Hz). IR (KBr disk): 1417s,
1331s and 820s cmϪ1. C28H28N2O4P2Pt requires C, 47.15; H,
3.95; N, 3.95. Found C, 47.10; H, 3.90; N, 3.30%.
Crystal data for fac-[Ir(BF2)3(CO)(PPh3)2] 3. M = 891.18,
orthorhombic, space group Pbca (no. 61), a = 9.9312(8), b =
18.493(2), c = 38.273(4) Å, U = 7029.4(11) Å3, T = 173(2) K,
Z = 8, µ(Mo-Kα) = 3.95 mmϪ1, 42025 reflections measured,
8046 unique (Rint = 0.049), final R1 = 0.036 (5930 data, I >
2σ(I)).
[Pt(PPh3)2(1,2-O2C2F2)] 5. A Young’s tap tube containing a
stirrer bead and a solution of [Pt(PPh3)2(η-C2H4)] (0.122 g,
0.163 mmol) in toluene (2 cm3) was frozen in liquid nitrogen
and evacuated. A sample of C2O2F2 (0.25 mmol) was then con-
densed into the Young’s tube which was resealed under vacuum,
allowed to warm to 0 ЊC by placing the tube in an ice bath and
the solution was stirred. After 30 min the reaction mixture
comprised an orange solution which was allowed to warm to
room temperature and stir for 48 h. After this time the reaction
mixture consisted of an orange solution and an off-white
precipitate. The solid was collected by vacuum filtration,
washed with toluene (1 cm3) and hexane (2 cm3) and then dried
by vacuum affording an off-white solid (0.064 g). NMR data
Crystal data for cis-[Pt(NO2)2(PPh3)2] 4. M = 837.63, tri-
¯
clinic, space group P1 (no. 2), a = 8.707(4), b = 10.872(5),
c = 14.645(8) Å, α = 85.32(3), β = 79.59(2), γ = 72.21(4)Њ,
U = 1297.7(11) Å3, T = 173(2) K, Z = 2, µ(Mo-Kα) = 5.93
mmϪ1, 13647 reflections measured, 5877 unique (Rint = 0.118),
final R1 = 0.065 (3552 data, I > 2σ(I)).
Crystal data for [Co(PMe3)4][BF4]. M = 267.82, cubic, space
group P213 (no. 198), a = 13.2859(6) Å, U = 2345.16(18) Å3,
T = 173(2) K, Z = 8, µ(Mo-Kα) = 1.52 mmϪ1, 15447 reflections
measured, 1814 unique (Rint = 0.118), final R1 = 0.031 (1459
data, I > 2σ(I)).
CCDC reference number 186/2190.
lographic files in .cif format.
1
(CD2Cl2): 31P-{1H} δ 8.2 (t, JPtP = 3806 Hz); 19F δ Ϫ64.9 (tt,
3
4JPF = 3, JPtF = 93 Hz); 13C-{1H} δ 136.5–128.0 (PPh3); 1H
δ 7.85–7.00 (PPh3) IR (KBr disk): ν(C–O) 1707, 1670 cmϪ1.
Satisfactory microanalytical data could not be obtained due to
the presence of impurities in the sample.
[Pt(dppb)(1,2-O2C2F2)] 6. A Young’s tap tube containing a
stirrer bead and a solution of [Pt(dppb)(η-C2H4)] (0.129 g,
0.198 mmol) in toluene (2 cm3) was frozen in liquid nitrogen
and evacuated. A sample of C2O2F2 (0.30 mmol) was then
condensed into the Young’s tube which was resealed under
vacuum, allowed to warm to 0 ЊC by placing the tube in an ice
bath and the solution was stirred. After 10 min the reaction
mixture comprised a pale precipitate and an orange solution
which was allowed to warm to room temperature and stir for
48 h. After this time the reaction mixture consisted of an orange
solution and an off-white precipitate. The solid was collected by
vacuum filtration, washed with toluene (1 cm3) and hexane
(2 cm3) and then dried by vacuum affording an off-white solid
Acknowledgements
We thank the EPSRC for research support and studentships
(G.R.W. and M.J.Q.) and N.C.N. thanks Laporte plc and
The Royal Society for additional supporting funds. Johnson
Matthey Ltd. are thanked for generous supplies of platinum
salts and we thank Jennifer Pardoe for providing samples of
B2F4.
Note added at proof: since the submission of this manuscript we
have noted a report (T. M. Peterson, J. T. Golden and R. C. Bergman,
Organometallics, 1999, 18, 2005) which provides spectroscopic data
1
1
(δB 23.9, JBF 160; δF Ϫ23.2, JBF 154 Hz) for a compound formulated
as [IrH(BF2)(PMe3)(η-C5Me5)].
1
(0.087 g). NMR data (CD2Cl2): 31P-{1H} δ 3.4 (t, JPtP = 3620
Hz); 19F δ Ϫ64.4 (tt, 4JPF = 3, 3JPtF = 90 Hz); 13C-{1H} δ 134.5–
1
128.5 (PPh3); H δ 7.75–7.10 (PPh3). IR (KBr disk): ν(C–O)
1706, 1669 cmϪ1. Satisfactory microanalytical data could not be
obtained due to the presence of impurities in the sample.
References
1 (a) G. Schmid, Angew. Chem., Int. Ed. Engl., 1970, 9, 819;
(b) G. J. Irvine, M. J. G. Lesley, T. B. Marder, N. C. Norman,
E. G. Robins, W. Roper, C. R. Rice, G. R. Whittell and L. J. Wright,
Chem. Rev., 1998, 98, 2685; (c) M. R. Smith, Prog. Inorg. Chem.,
1999, 48, 505; (d) H. Braunschweig, Angew. Chem., Int. Ed., 1998,
37, 1787.
2 T. B. Marder and N. C. Norman, Topics in Catalysis, eds. W. Leitner
and D. G. Blackmond, Baltzer Science Publishers, Amsterdam,
1998, vol. 5, p. 63; I. Beletskaya and A. Pelter, Tetrahedron, 1997,
53, 4957; K. Burgess and M. J. Ohlmeyer, Chem. Rev., 1991, 91,
1179; K. Burgess and W. A. van der Donk, in Encyclopedia
X-Ray crystallography
Crystallographic data for compound 1 are given in ref. 5. For
2–4 and [Co(PMe3)4][BF4] X-ray diffraction measurements
were carried out on single crystals coated in a hydrocarbon
oil mounted on a glass fibre under argon, using graphite-
monochromated Mo-Kα radiation (λ = 0.71073 Å) on a Bruker
SMART area detector diffractometer, and the structures
4036
J. Chem. Soc., Dalton Trans., 2000, 4032–4037