Template controlled synthesis of a coordinated [11]ane-P2C NHC macrocycle

Article abstract of DOI:10.1039/b617033a

Rhenium complex [5]Cl with the coordinated [11]ane-P₂C ^NHC macrocycle was obtained by a metal template controlled ring formation reaction; in this reaction a coordinated NH,NH-stabilised imidazolidin-2-ylidene ligand was connected vi

Full text of DOI:10.1039/b617033a

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Template controlled synthesis of a coordinated [11]ane-P2CNHC
macrocycle{
Oliver Kaufhold,a Andreas Stasch,b Peter G. Edwards*b and F. Ekkehardt Hahn*a
Received (in Cambridge, UK) 22nd November 2006, Accepted 17th January 2007
First published as an Advance Article on the web 8th February 2007
DOI: 10.1039/b617033a
Rhenium complex [5]Cl with the coordinated [11]ane-P2CNHC
Macrocycles containing N-heterocyclic carbenes (NHCs) are
almost unknown.10 The complex dication with a cyclic tetra-
macrocycle was obtained by a metal template controlled ring
carbene ligand E (Scheme 1) was obtained by a template controlled
cyclisation of b-functionalised phenylisocyanide11 followed by
bridging alkylation of the NH,NH-stabilised carbene ligands at a
PtII centre.12 In addition, ligands derived from cyclophanes
containing two NHC donors are known13 but by definition they
are not considered macrocycles.2
formation reaction; in this reaction a coordinated NH,NH-
stabilised imidazolidin-2-ylidene ligand was connected via the
nitrogen atoms to two phenyl substituents of a 2-fluorophenyl
substituted diphosphine ligand.
Tridentate macrocycles such as tacn A (Scheme 1, tacn =
triazacyclononane1) coordinate in a facial manner in octahedral
complexes with the remaining coordination sites in cis positions to
each other and trans to the donor atoms of the macrocycle.
Compared to complexes with acyclic and/or monodentate ligands,
complexes with macrocyclic ligands having the same donor set
gain additional stability from the macrocyclic effects.2 Besides A
featuring amine donor groups more recently the synthesis and
coordination chemistry of triphosphorus macrocycles has been
investigated. Complexes containing 9-,3 10-,4 11-5 and 12-6
membered macrocyclic P3 ligands are known. Gladysz and co-
workers reported the synthesis of a complex with a 45-membered
P3 macrocycle by ring closing metathesis at a tungsten template.7
Only triphosphines of type B8 (mixture of all possible
diastereoisomers) and C9 obtained by alkylation of the tripho-
sphine ligand in [(CO)3Mo([12]ane-P3H3)]6e followed by oxidative
decomplexation (Scheme 1) have been isolated as free ligands.
Macrocycles of type D have so far only been obtained as
triphosphine oxides3a while some derivatives of type C have been
liberated by reductive methods from their FeII complexes.6a
The similarities in the donor properties of phosphines and
NHCs makes the preparation of ligands with a mixed phosphine/
NHC donor set an interesting preparative target. While pincer
complexes with mixed R3P/NHC ligands have been described,14
we report here on the template controlled synthesis of the
rhenium(I) complex [5]Cl with the novel macrocyclic PPC-ligand
[11]ane-P2CNHC (Scheme 2).
The macrocycle [11]ane-P2CNHC in complex [5]Cl was synthe-
sised by a template controlled cyclisation reaction. Initially, an easy
to functionalise NH,NH-stabilised carbene ligand was generated at
the rhenium(I) template (complex [1]) followed by the introduction
of diphosphine 3 to give complex [4]Cl. Subsequently the
coordinated diphosphine and the NH,NH-stabilised carbene
ligand were connected via two new N–C bonds leading to the
complex with the macrocyclic ligand.
Scheme 1 Macrocycles with triamine, triphosphine and NHC-donor set.
aInstitut fu¨r Anorganische und Analytische Chemie, Universita¨t
Mu¨nster, Corrensstraße 36, D-48149, Mu¨nster, Germany.
E-mail: fehah@uni-muenster.de; Fax: +49-251-833-3108
bSchool of Chemistry, Cardiff University, Cardiff, UK CF10 3AT.
E-mail: edwardspg@cardiff.ac.uk; Fax: +44-29-2087-4083
{ Electronic supplementary information (ESI) available: Preparation of
[1], 2, 3, [4]Cl and [5]Cl, molecular plots of [1] and 3 and details of the
crystal structure solutions for compounds [1], 3, [4]Cl?3THF and
[5]Cl?3H2O. See DOI: 10.1039/b617033a
Scheme 2 Reagents and conditions: (i) as described,17 THF, 25 uC, 12 h;
(ii) 1. Et2O, 278 uC 4 h, 2. 25 uC, 12 h; (iii) CH3CN, reflux, 6 h; (iv) THF,
KOt-Bu, 25 uC, 5 d.
1822 | Chem. Commun., 2007, 1822–1824
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Complexes containing NH,NH-stabilised benzimidazolin-2-
ylidenes11,12,15 and imidazolidin-2-ylidenes16 are accessible from
complexes with b-functionalised isocyanides. The NH,NH-sub-
stituted carbene ligands are easily N,N9-alkylated.11,12,16
Alternatively, complex [1] bearing an NH,NH-stabilised carbene
ligand was prepared by reaction of b-aminoethylphosphinimine
and [ReCl(CO)5] following a procedure described by Liu et al.17
(Scheme 2). We assume that this reaction proceeds by formation of
triphenylphosphine oxide and coordinated b-aminoethyl isocya-
nide by deoxygenation of a carbonyl ligand. Subsequently the
b-aminoethyl isocyanide ligand reacts under intramolecular
cyclisation to give the complex with the NH,NH-stabilised carbene
ligand.16
Fig. 1 Molecular structure of complex cation [4]+ in [4]Cl?3THF.
˚
Selected bond lengths (A) and angles (u): Re–P1 2.428(2), Re–P2
Surprisingly, the IR spectrum of [1] shows two N–H stretching
frequencies at n = 3429 and 3265 cm21. { This observation is due
to an intermolecular hydrogen bond between a NH-proton and a
chloro ligand from an adjacent molecule. The crystal structure
analysis of [1]§ (see ESI{) confirms the existence of such an
2.420(2), Re–C1 2.188(5), Re–C4 1.971(5), Re–C5 1.950(5), Re–C6
1.975(6); P1–Re–P2 80.11(5), P1–Re–C1 90.60(13), P1–Re–C4 93.54(14),
P1–Re–C5 90.50(15), P1–Re–C6 173.31(14), P2–Re–C1 90.43(13), P2–Re–
C4 173.60(14), P2–Re–C5 91.53(15), P2–Re–C6 93.21(15).
The X-ray diffraction analysis with crystals of [5]Cl?3H2O§
(Fig. 2) confirms the formation of the coordinated macrocycle
[11]ane-P2CNHC. All bond distances in [5]+ are shortened in
comparison to equivalent bonds in [4]+. This is most noticeable for
the Re–C1 and Re–P bonds. The bond angles in the cation [5]+
deviate more strongly from octahedral geometry than those found
for the cation [4]+. This effect is most pronounced for those angles
involving donor groups of the macrocycle. For example, the
P–Re–C1 bond angles in the cation [4]+ (P1–Re–C1 90.60(13)u,
P2–Re–C1 90.43(13)u) are nearly orthogonal whereas significant
smaller values for the equivalent angles were found in the cation
[5]+ (P1–Re–C1 77.96(10)u, P2–Re–C1 79.12(10)u).
We have shown that the coordinated PPC macrocycle [11]ane-
P2CNHC can be obtained in a template controlled reaction of a
tricarbonylrhenium(I) complex containing a NH,NH-stabilised
carbene ligand and a 2-fluorophenyl substituted diphosphine
ligand. The novel PPC macrocycle should have similar useful
properties as its NNN and PPP analogues. Encouraging
preliminary results indicate, that the macrocycle synthesis can be
transferred to other template metals. Further experiments regard-
ing the liberation of the macrocyclic ligand from the metal centre
as well as the generation of this and similar hetero-donor
phosphine/carbene macrocycles on catalytically active metal
centres are in progress.
…
˚
intermolecular hydrogen bond (NH Cl distance 2.386 A). Similar
18
…
carbene-NH Cl interactions have been described.
The chelating diphosphine 319 was prepared from 1,2-bis(di-
chlorophosphino)benzene20 and ortho-lithiated fluorobenzene. The
molecular structure of 3§ is described in the ESI.{ Reaction of [1]
with 3 in refluxing acetonitrile leads to the substitution of the
chloro ligand as well as of one CO ligand in nearly quantitative
yield (98%) and formation of [4]Cl (Scheme 2). Complex [4]Cl has
been characterised by spectroscopy{ and X-ray crystallography.§
The IR spectrum of [4]Cl exhibits only one weak N–H
absorption at n = 3460 cm21. The 13C{1H} NMR spectrum
shows the resonance of the carbene carbon atom at d 189.8. This
signal is split into a triplet (2JCP = 9.8 Hz) by coupling with both
phosphorus atoms in the cis positions. The resonance of the
carbonyl carbon atom trans to the carbene ligand is observed at d
190.0 as a broad multiplet. The remaining CO ligands give rise to a
signal at d 191.0 which is observed as a doublet of doublets due to
the coupling with the phosphorus atoms (2JCP-trans = 52 Hz,
2JCP-cis = 8 Hz ) of the diphosphine ligand. Inversion of the
phosphorus atoms is prevented by coordination of the diphosphine
resulting in two chemical inequivalent phenyl rings and thereby
generating two chemical inequivalent fluorine atoms.
Consequently, the 19F NMR spectrum exhibits two resonances
at d 2100 and 298.
The X-ray diffraction analysis of [4]Cl?3THF (Fig. 1)§ confirms
the expected facial arrangement of the ligands in a distorted
octahedral complex. Bond length and angles in the cation [4]+ fall
in the expected range. The plane of the carbene ligand is orientated
between P1/P2 and C4/C6 in a manner which allows a minimal
interaction with the coordinated diphosphine.
Addition of KOt-Bu to a suspension of [4]Cl in THF leads
within five days to a clear solution from which the light yellow
complex [Re(CO)3([11]ane-P2CNHC)]Cl [5]Cl precipitates in 90%
yield (Scheme 2). The imidazolidin-2-ylidene in [5]+ is no longer
able to rotate around the Re–C bond after formation of the
macrocycle. Hence, the diastereotopic CH2–CH2 protons of the
backbone give rise to two resonances at d 4.61 and 3.15, which
Fig. 2 Molecular structure of complex cation [5]+ in [5]Cl?3H2O.
˚
Selected bond lengths (A) and angles (u): Re–P1 2.3957(13), Re–P2
3
appear as multiplets by geminal und J coupling (AA9BB9 spin
2.3895(14), Re–C1 2.172(4), Re–C34 1.966(4), Re–C35 1.950(4), Re–C36
1.966(4); P1–Re–P2 81.58(5), P1–Re–C1 77.96(10), P1–Re–C34 91.72(13),
P1–Re–C35 97.93(12), P1–Re–C36 167.33(12), P2–Re–C1 79.12(10), P2–
Re–C34 170.73(13), P2–Re–C35 96.60(11), P2–Re–C36 91.15(13).
system).{ NOE experiments confirm that the downfield resonance
at d 4.61 can be assigned to the protons interacting with the
anisotropy cone of the central bridging phenyl ring.
This journal is ß The Royal Society of Chemistry 2007
Chem. Commun., 2007, 1822–1824 | 1823

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1 P. Chaudhuri and K. Wieghardt, Prog. Inorg. Chem., 1987, 35, 329.
Notes and references
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{ Spectroscopic data for [1], 2, 3, [4]Cl and [5]Cl. [1]: NMR: 1H (400.1 MHz,
CDCl3): d 6.90 (s, br, 2H, NH), 3.72 (s, 4H, NCH2CH2N); 13C{1H}
(100.6 MHz, CDCl3): d 193.6 (NCN), 186.8 (CO), 184.9 (CO), 184.7 (CO),
44.2 (NCH2CH2N); IR (KBr): n 3429 (s, NH), 3265 (s, br, NH), 2107 (s,
CO), 2016 (s, CO), 1993 (s, br, CO), 1924 cm21 (s, br, CO); ES-MS+: m/z
(%): 426.9455 (100) (calc. [C7H6N2ClO4Re + Na]+ 426.9457). 2: NMR:
13C{1H} (100.6 MHz, CDCl3): d 144.6 (d, JPC = 13 Hz, Ar–Cipso), 133.8
1
2
(Ar–Cmeta), 131.1 (d, JPC = 9 Hz, Ar–Cortho); 31P{1H} (162.0 MHz,
CDCl3): d 151. 3: NMR: 1H (400.1 MHz, CDCl3, assignment, see
Scheme 2): d 7.33 (m, 2H, Ar–H3), 7.31 (m, 4H, Ar–H7), 7.14 (m, 2H, Ar–
H2), 7.04 (m, 4H, Ar–H6), 7.00 (m, 4H, Ar–H8), 6.92 (m, 4H, Ar–H5);
13C{1H} (100.6 MHz, CDCl3, assignment, see Scheme 2): d 164.1 (d, 1JCF
= 264 Hz, Ar–C9), 140.7 (m, Ar–C1), 134.7 (m, Ar–C5), 133.9 (m, Ar–C2),
3
3
131.1 (d, JCF = 8.3 Hz, Ar–C7), 129.9 (Ar–C3), 124.4 (d, JCP = 2.7 Hz,
Ar–C6), 122.7 (m, Ar–C4), 115.2 (d, JCF = 23.2 Hz, Ar–C8); 31P{1H}
2
(162.0 MHz, CDCl3): d 236 (m); 19F (376.5 MHz, CDCl3): d 2103 (m);
ES-MS+: m/z (%): 541.0872 (100) (calc. [C30H20F4P2 + Na]+ 541.0869),
519.1062 (18) (calc. [C30H20F4P2 + H]+ 519.1055). [4]Cl: NMR: 1H
(400.1 MHz, CD3CN, assignment, see Scheme 2): d 8.02 (m, 2H, Ar–H4),
7.88 (m, 2H, Ar–H5), 7.67 (m, 2H, Ar–H9), 7.44 (m, 2H, Ar–H15), 7.39
(m, 2H, Ar–H10), 7.32 (m, 2H, Ar–H11), 7.27 (m, 2H, Ar–H8), 7.16 (m,
2H, Ar–H16), 7.10 (m, 2H, Ar–H14), 6.92 (m, 2H, Ar–H17), 6.56 (s, 2H,
NH), 3.21 (s, 4H, NCH2CH2N); 13C{1H} (100.6 MHz, CD3CN, assign-
2
2
ment, see Scheme 2): d 191.0 (dd, JCP-trans = 50.4 Hz, JCP-cis = 8.2 Hz,
COcis-C1), 190.0 (m, br, COtrans-C1), 189.8 (t, JCP = 9.8 Hz, C1), 164.5 (d,
2
1JCF = 249 Hz, C7), 163.4 (dd, 1JCF = 247 Hz, 2JCP = 4.9 Hz, C13), 139.2
(dd, 1JCP = 48.5 Hz, 2JCP = 33.4 Hz, C3), 136.8 (dd, 2JCP = 14.0 Hz, 3JCP
=
2.5 Hz, C4), 136.8 (m, C11), 136.6 (dd, 3JCF = 9.5 Hz, 4JCP = 2.0 Hz, C9),
134.9 (dd, JCF = 8.5 Hz, JCP = 1.6 Hz, C15), 134.8 (dd, JCP = 6.2 Hz,
9 P. G. Edwards, J. S. Fleming and S. S. Liyanage, Inorg. Chem., 1996,
35, 4563.
3
4
3
4JCP = 2.2 Hz, C5), 133.0 (m, C17), 126.5 (dd, JCP = 11.2 Hz, JCF
=
3
4
10 F. E. Hahn, Angew. Chem., Int. Ed., 2006, 45, 1348.
11 (a) F. E. Hahn, V. Langenhahn, N. Meier, T. Lu¨gger and
W. P. Fehlhammer, Chem.–Eur. J., 2003, 9, 704; (b) F. E. Hahn,
C. Garc´ıa Plumed, M. Mu¨nder and T. Lu¨gger, Chem.–Eur. J., 2004, 10,
6285.
3
4
3.0 Hz, C10), 125.6 (dd, JCP = 8.3 Hz, JCF = 3.0 Hz, C16), 122.2 (ddd,
1JCP = 53 Hz, 2JCF = 17 Hz, 4JCP = 2.0 Hz, C12), 118.2 (dd, 2JCF = 23.8 Hz,
3JCP = 3.4 Hz, C8), 117.3 (ddd, JCP = 45 Hz, JCF = 16.4 Hz, JCP
=
1
2
4
2
3
2.8 Hz, C6), 117.0 (dd, JCF = 23.0 Hz, JCP = 3.7 Hz, C14), 45.9 (C2);
31P{1H} (162.0 MHz, CDCl3): d 22 (d); 19F (376.5 MHz, CD3CN): d 298,
2100; IR (KBr): n 3460 (w, NH), 2043 (s, CO), 1971 (s, CO), 1949 (s, CO);
ES-MS+: m/z (%): 859.0893 (100) (calc. [C36H26N2F4O3P2Re]+ 859.0909).
12 F. E. Hahn, V. Langenhahn, T. Lu¨gger, T. Pape and D. Le Van, Angew.
Chem., Int. Ed., 2005, 44, 3759.
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D. H. Brown, R. A. Haque, B. W. Skelton and A. H. White, Dalton
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111; (e) J. C. Garrison, R. S. Simons, C. A. Tessier and W. J. Youngs,
J. Organomet. Chem., 2003, 673, 1; (f) R. S. Simons, J. C. Garrison,
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43, 3423; (g) J. C. Garrison, R. S. Simons, J. M. Talley, C. Wesdemiotis,
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15 (a) M. Basato, R. A. Michelin, M. Mozzon, P. Sgarbossa and A. Tassan,
J. Organomet. Chem., 2005, 690, 5414; (b) R. A. Michelin, A. J. L.
Pombeiro and M. F. C. Guedes da Silva, Coord. Chem. Rev., 2001, 218,
75; (c) M. Basato, F. Benetollo, G. Facchin, R. A. Michelin,
M. Mozzon, S. Pugliese, P. Sgarbossa, S. M. Sbovata and A. Tassan,
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16 F. E. Hahn, V. Langenhahn and T. Pape, Chem. Commun., 2005, 5390.
17 C.-Y. Liu, D.-Y. Chen, G.-H. Lee, S.-M. Peng and S.-T. Liu,
Organometallics, 1996, 15, 1055.
1
[5]Cl: NMR: H (400.1 MHz, CD3CN, assignment, see Scheme 2): d 7.83
(m, 2H, Ar–H5), 7.81 (m, 2H, Ar–H4), 7.69 (m, 2H, Ar–H13), 7.66 (m, 2H,
Ar–H9), 7.63 (m, 2H, Ar–H16), 7.39 (m, 2H, Ar–H14), 7.38 (m, 2H, Ar–
H15), 7.37 (m, 2H, Ar–H8), 7.25 (t, 2H, Ar–H10), 6.97 (m, 2H, Ar–H11),
4.61 (m, 2H, N–C(2)H–C(2)H–N), 3.15 (m, 2H, N–C(2)H–C(2)H–N);
13C{1H} (100.6 MHz, CD3CN, assignment, see Scheme 2): d 193.4 (br,
COtrans-C1), 192.3 (t, 2JCP = 13.8 Hz, C1), 191.1 (dm, 2JCP-trans 46.0, COcis-
C1), 164.4 (dd, 1JCF = 249 Hz, 2JCP = 5.0 Hz, C7), 145.8 (d, 2JCP = 11.8 Hz,
Ar–C17), 139.9 (m, Ar–C3), 136.6 (d, 3JCF = 9.2 Hz, Ar–C9), 136.2 (m, Ar–
2
C4), 134.7 (d, JCP = 1.6 Hz, Ar–C13), 134.6 (m, Ar–C5), 134.3 (m, Ar–
C11) 131.2 (d, 4JCP = 1.6 Hz, Ar–C15), 127.4 (d, 3JCP = 8.3 Hz, Ar–C14),
3
126.8 (m, Ar–C10), 125.6 (d, JCP = 6.3 Hz, Ar–C16), 123.8 (dd, JCP
1
=
56.4 Hz, 4JCF = 4.9 Hz, Ar–C12), 117.8 (dd, 2JCF = 21.9 Hz, 3JCP = 4.2 Hz,
1
2
Ar–C8), 115.1 (dd, JCP = 54.6 Hz, JCF = 17.7 Hz, Ar–C6), 52.4
(NCH2CH2N); 31P{1H} (162.0 MHz, CD3CN): d 16 (d); 19F (376.5 MHz,
CD3CN): d 297 (m); IR (KBr): n 2031 (s, CO), 1963 (s, CO), 1937 (s, CO);
ES-MS+: m/z (%): 819.0770 (100) (calc. [C36H24N2F2O3P2Re]+: 819.0784).
§ Crystal data for [4]Cl?3THF and [[5]Cl?3H2O]: C48H50N2ClF4O6P2Re
¯
¯
[C36H30N2ClF2O6P2Re], M = 1110.49 [908.21], triclinic [triclinic], P1 [P1],
a = 11.201(5) [9.030(5)], b = 11.800(5) [10.898(5)], c = 20.504(5)
˚
[19.929(5)] A, a = 92.239(5) [75.388(5)], b = 100.058(5) [82.356(5)], c =
3
˚
117.123(5) [68.013(5)]u, V = 2353.1(2) [1758.1(13)] A , T = 150(2) [150(2)] K,
l = 0.71073 [0.71073] A, Z = 2 [2], m = 2.773 [3.682] mm21, 16653 [11370]
˚
data measured, 9183 [7588] unique data, R = 0.0415 [0.0308], wR = 0.0987
[0.0660] for 8650 [6915] data [I ¢ 2s(I)]. Crystal data for 3 and [[1]]:
C30H20F4P2 [C7H6N2ClO4Re], M = 518.40 [403.79], monoclinic [mono-
clinic], P21/c [P21/c], a = 10.966(2) [8.852(2)] , b = 14.272(3) [10.297(2)], c =
3
15.942(3) [12.389(3)] A, b= 91.88(3) [107.84(3)], V = 2493.8(9) [1075.0(4)] A ,
˚
˚
18 F. E. Hahn, T. Lu¨gger and M. Beinhoff, Z. Naturforsch., B: Chem. Sci.,
2004, 59, 196.
19 T. Albers, PhD thesis, 2001, Cardiff University.
20 (a) E. P. Kyba, S.-T. Liu and R. L. Harris, Organometallics, 1983, 2,
1877; (b) E. P. Kyba, M. C. Kerby and S. P. Rines, Organometallics,
1986, 5, 1189.
˚
T = 150(2) [150(2)] K, l = 0.71073 [0.71073] A, Z = 4 [4], m = 0.222
[11.547] mm21, 8965 [3540] data measured, 4630 [2315] unique data, R =
0.0457 [0.0264], wR = 0.0950 [0.0596] for 3481 [2070] data [I ¢ 2s(I)].
CCDC 624140 (3), 624141 ([1]), 624142 ([4]Cl?3THF) and 424143
([5]Cl?3H2O). For crystallographic data in CIF or other electronic format
see DOI: 10.1039/b617033a
1824 | Chem. Commun., 2007, 1822–1824
This journal is ß The Royal Society of Chemistry 2007