Council and for an Australian Postgraduate Award (to S. E.
W.).
Notes and references
†
1, [H(oPtacn)][PF ]ؒ0.5H O (Found: C, 57.91; H, 6.47; N, 6.60.
6 2
C H N P F ؒ0.5H O requires C, 57.94; H, 6.90; N, 6.54%); δ (CDCl )
3
1
43
3
2
6
2
P
3
Ϫ14.22 (s), Ϫ143.78 [sept, J(PF) 707 Hz]; δ (CDCl ) 7.37–7.32 (8 H,
H
3
m), 7.24–7.17 (5 H, m), 6.90–6.85 (1 H, m), 3.97 (2 H, d), 3.11 (2
H, sept), 3.00–2.93 (4 H, m), 2.79 (8 H, br s), 1.21 (6 H, d), 1.14 (6 H, d);
ϩ
m/z (ES-MS) 488 {[H(oPtacn)] }.
‡
2, [Cu(oPtacn)][PF ] (Found: C, 52.62; H, 6.41; N, 6.10. C H -
6
3
1
4
2
N P F Cuؒ0.5H O requires C, 52.80; H, 6.15; N, 5.96%); δ [(CD ) CO]
3
2
6
2
P
3 2
Ϫ0.3 (br s), Ϫ142.00 [sept J(PF) 707 Hz]; δ [(CD ) CO] 7.65–7.50 (8
H
3 2
H, m), 7.50–7.45 (5 H, m), 6.94 (1 H, t), 3.88 (2 H, s), 3.39 (2 H, sept),
3
{
§
.15–2.55 (12 H, m), 1.47 (6 H, d), 1.13 (6 H, d); m/z (ES-MS) 550
[Cu(oPtacn)] }.
ϩ
Crystal data for 2: C H CuF N P , M = 696.2, monoclinic, space
3
1
42
6
3
2
group P2 /c, a = 15.091(6), b = 14.532(3), c = 17.990(9) Å,
1
3
Ϫ1
β = 123.87(2)Њ, U = 3276(2) Å , Z = 4, D = 1.41 g cm , Enraf-Nonius
c
–
1
CAD-4 diffractometer, µ(Mo-Kα: λ = 0.71073 Å) = 8.21 cm ,
F(000) = 1448.0, T = 294 K, final R = 0.037, R = 0.051 for 2821
w
observed data [I > 3σ(I), 2θ < 46Њ]. CCDC reference number 186/1414.
See http:/www.rsc.org/suppdata/dt/1999/1539/ for crystallographic files
in .cif format.
¶
3, [PtCl {H(oPtacn)} ][PF ] (Found: C, 48.07, H, 5.33, N, 5.13.
2 2 6 2
Fig. 1 Drawing of the complex cation 2 showing the 20% thermal
ellipsoids.
C H N P Cl F PtؒH O requires C, 48.06, H, 5.72, N, 5.42%);
δ [(CD ) CO] 15.44 [s, J(PPt) 2597], Ϫ142.05 [sept, J(PF) 707 Hz];
P
6
2
86
6
4
2
12
2
3 2
δ [(CD ) CO] 7.95–7.75 (10 H, m), 7.65–7.45 (14 H, m), 7.29 (2 H, t),
H
3 2
3
1
in the P NMR spectrum. In sum this evidence leads to the
structure for 3 in Scheme 1.
7.09 (2 H, q), 4.50 (4 H, s), 3.35 (4 H, sept), 3.27 (4 H, m), 3.10–2.60 (20
H, m), 1.30 (12 H, d), 1.18 (12 H, d); m/z (ES-MS) 1387 ([PtCl {H-
2
ϩ
2ϩ
(
oPtacn)} ϩ PF ] ), 621 ([PtCl {H(oPtacn)} ] ).
Addition of base frees the macrocyclic centres in 3 and allows
selective formation of trimers. For example, reaction of 3 with
triethylamine and [Cu (OAc) (H O) ] gave [PtCl {oPtacn-
2 6 2 2
|
| 4, [PtCl {(oPtacn)[Cu(OAc)]} ][PF ] (Found: C, 44.08, H, 4.99,
2
2
6
2
N, 4.43. C H N O P Cl F Cu PtؒH O requires C, 44.17, H, 5.17,
6
6
90
6
4
4
2
12
2
2
2
4
2
2
2
N, 4.68%); inductively-coupled-plasma analysis (±10%): ratio
[
Cu(OAc)]} ][PF ] , 4, in 56% yield. The base is essential in the
3
Ϫ1
Ϫ1
2
6 2
Cu:P:Pt = 2.0:3.6:0.9; λmax/nm (MeCN) 661 (ε/dm mol cm 797);
preparation of this heterometallic trimer; whilst the coordin-
ation of “soft” Pt() and Cu() ions by the phosphine group in
oPtacn is relatively facile, coordination of the “hard” Cu() ion
requires deprotonation of the macrocyclic domain and, there-
fore, is pH dependent. Partial analytical data for C, H and N
and data for the Cu:P:Pt ratio agree with the formulation of 4,
as does the ES mass spectrum which shows a prominent peak at
EPR (MeCN, 77 K): g 2.25 (A 164 G), g 2.07; δ [(CD ) CO] Ϫ141.97
|
|
||
⊥
P
3 2
[
sept,
J(PF)
707
Hz];
m/z
(ES-MS)
743
([PtCl2-
2
ϩ
{(oPtacn)[Cu(OAc)]}2] ).
1 Y. Ishii, K. Miyashita, K. Kamita and M. Hidai, J. Am. Chem. Soc.,
1997, 119, 6448.
2
3
4
E. Kimura, Y. Kodama, M. Shionoya and T. Koike, Inorg. Chim.
Acta, 1996, 246, 151.
A. Carroy, C. R. Langick, J.-M. Lehn, K. E. Matthes and D. Parker,
Helv. Chim. Acta, 1986, 69, 580.
2ϩ
7
43 m/z for the molecular ion (M ).|| The UV/VIS spectrum
reveals a band at 661 nm with a distinct low energy tail and
an axial EPR spectrum is observed. These spectroscopic data
closely match those of a similar crystallographically-char-
acterised N O -coordinated copper() complex and are indic-
ative for isolated mononuclear copper() centres with distorted
square-pyramidal coordination. The structure proposed for 4 in
Scheme 1 is consistent with these results.
We have shown that reductive amination of nitrogen macro-
cycles with (diphenylphosphino)benzaldehydes provides a con-
venient synthesis of novel phosphino-substituted macrocycles.
The ligating properties of multinucleating ligands of this
type can be tuned by varying the relative orientation of the
phosphine and macrocycle groups by changing from ortho to
meta or para aryl substitution. Studies of other heterometallic
oligomers, including those bridged by the obligatory binucle-
ating meta-analogue of oPtacn [prepared from 3-(diphenyl-
phosphino)benzaldehyde ] and, as well, with new ligands
derived from other secondary amines, are underway. The chal-
lenge to demonstrate novel reactivities for these heterometallic
oligomers remains.
K. P. Wainwright, Coord. Chem. Rev., 1997, 166, 35; L. Spiccia,
B. Graham, M. T. W. Hearn, G. Lazarev, B. Moubaraki, K. S.
Murray and E. R. T. Tiekink, J. Chem. Soc., Dalton Trans., 1997,
4089; S. Mahapatra, S. Kaderli, A. Llobet, Y.-M. Neuhold,
T. Palanché, J. A. Halfern, V. G. Young, Jr., T. A. Kaden, L. Que, Jr.,
A. D. Zuberbühler and W. B. Tolman, Inorg. Chem., 1997, 36, 6343;
L. J. Farrugia, P. A. Lovatt and R. D. Peacock, J. Chem. Soc., Dalton
Trans., 1997, 911; A. Sokolowski, J. Müller, T. Weyhermüller,
R. Schnepf, P. Hildebrandt, K. Hildenbrand, E. Bothe and
K. Wieghardt, J. Am. Chem. Soc., 1997, 119, 8889; M. Di Vaira,
F. Mani and P. Stoppioni, Inorg Chim. Acta, 1998, 273, 151.
D. Ellis, L. J. Farrugia, D. T. Hickman, P. A. Lovatt and R. D.
Peacock, Chem. Commun., 1996, 1817.
9
3
2
5
6 H. Hope, M. Viggiano, B. Moezzi and P. P. Power, Inorg. Chem.,
1984, 23, 2550.
7 (a) J. A. Halfern and W. B. Tolman, Inorg. Synth, 1998, 32, 75;
7c
(
(
b) T. B. Rauchfuss and D. A. Wrobleski, Inorg Synth., 1982, 21, 175;
c) G. P. Schiemenz and H. Kaack, Liebigs Ann. Chem., 1973,
1
480.
R. D. Köhn, G. Seifert and G. Kociok-Köhn, Chem. Ber., 1996, 129,
327.
8
9
1
P. Bradford, R. C. Hynes, N. C. Payne and C. J. Willis, J. Am. Chem.
Soc., 1990, 112, 2647.
Acknowledgements
We are grateful for support from the Australian Research
Communication 9/01885I
1
540
J. Chem. Soc., Dalton Trans., 1999, 1539–1540