Wei et al.
maceutical reagents.6 Examples of these cores include the
application of such reagents and led to consideration of other
ligand sets, as well as core structures. Consequently, the
{MO}3+ core has been investigated with mixed NxPy and
SxPy ligands22-24 as well as N4 donor types.25 Another strategy
for the synthesis of neutral complexes with the {MO}3+ core
employs a mixed-ligand set of a tridentate dithiolate of the
type (S-X-S)2- (where X ) O, S, or NR) and a mono-
dentate thiolate, hence the description “3 + 1” mixed-ligand
complexes.26-28 A serious drawback to this approach is the
tendency of the 3 + 1 system to undergo further substitution
reactions in vivo, presumably to achieve a closed shell,29
and the lability of the monodentate ligand in the presence
of competing ligating functions.
metal oxo unit {MVO}3+, the metal nitrido group {MVN}2+,7
the metal hydrazino moiety {M(HxNNR)n}m+ 8,9
and the
,
metal tricarbonyl core {MI(CO)3}+,10,11 of which the metal
oxo core is the most extensively developed. The {MO}3+
subunit is stabilized by π-donating alkoxide and thiolate
ligands. Consequently, compounds of the {MVO}3+ core with
NxS4-x tetradentate ligands with square-pyramidal geometry
have been extensively investigated. These include N4 pro-
pyleneamine oxime (PnAO),12 N3S triamidomonothiols,13
N2S2 diamidodithiols (DADSs),14 N2S2 monoaminomono-
amidodithiols (MAMAs),15 and diaminodithiols (DADTs),16
including numerous examples of tripeptides and tetrapeptides
appropriately derivatized to act as bifunctional chelators.
While the {MO}3+ core is robust and readily accessible by
As part of our continuing investigations of the coordination
chemistry of the oxorhenium(V) core, we have investigated
the chemistry of {ReO}3+ with efficient chelating ligands
which may provide platforms for further derivatization. It is
noteworthy that {ReVO}3+ is a redox-active moiety which
-
reduction of the parent MO4 , the inevitable formation of
multiple isomers with NxS4-x ligand types17-21 differing in
their pharmacokinetic properties has hindered the widespread
(6) Banerjee, S. R.; Francesconi, L.; Valliant, J. F.; Babich, J. W.; Zubieta,
J. Nucl. Med. Biol., in press.
(18) Numerous examples of peptide-based bifunctional chelators for the
{TcVO}3+ core have been described in recent years. Representative
examples include (i) MAG3 types (MAG3 ) mercaptoacetylglycyl-
glycylglycine) [(a) Liu, S.; Edwards, D. S.; Looby, R. J.; Poirier, M.
J.; Rajopadhye, M.; Bourque, J. P.; Carroll, T. R. Bioconjugate Chem.
1996, 7, 196. (b) Kasina, S.; Sanderson, J. A.; Fitzner, J. N.; Srinivasan,
A.; Rao, T. N.; Hobson, L. J.; Reno, J. M.; Axworthy, D. B.; Beaumier,
P. L.; Fritzberg, A. R. Bioconjugate Chem. 1998, 9, 108. (c) Zhu, Z.;
Wang, Y.; Zhang, Y.; Liu, G.; Liu, N.; Rusckowski, M.; Hnatowich,
D. J. Nucl. Med. Biol. 2001, 28, 703 and references therein. (d) Van
Domselaar, G. H.; Okarvi, S. M.; Fanta, M.; Suresh, M. R.; Wishart,
D. S. J. Labelled Compd. Radiopharm. 2000, 43, 1193], (ii) other
cysteine-containing tripeptides and derivatives [(e) Goodbody, A.;
Pollak, A. Peptide-chelator conjugates for diagnostic imaging. PCT
Int. Appl. 1995; p 22. (f) Pollak, A.; Goodbody, A. E.; Ballinger, J.
R.; Duncan, G. S.; Tran, L. L.; Dunn-Dufault, R.; Meghji, K.; Lau,
F.; Andrey, T. W. Nucl. Med. Commun. 1996, 17, 132. (g) Lister-
James, J.; Knight, L. C.; Mauer, A. H.; Bush, L. R.; Moyer, B. R.;
Dean, R. T. J. Nucl. Med. 1996, 37, 775. (h) Pearson, D. A.; Lister-
James, J.; McBride, W. J.; Wilson, D. M.; Martel, L. J.; Civitello, E.
R.; Taylor, J. E.; Moyer, B. R.; Dean, R. T. J. Med. Chem. 1996, 39,
1361. (i) Wishart, D. S. Biotechnology (2nd Ed.). 1991- 2001, 5b,
325], and (iii) Gly-Ala-Gly-Gly peptide [(j) Ben-Haim, S.; Kahn, D.;
Weiner, G. J.; Madsen, M. T.; Waxman, A. D.; Williams, C. M.;
Maguire, R. T. Nucl. Med. Biol. 1994, 21, 131]. (k) Luyt, L. G.; Hunter,
D. H. Technetium-99m labeling of tamoxifen and lysine derivatives
using an N2S2 bifunctional chelator: Single isomer radiopharma
ceuticals. Book of Abstracts, 217th ACS National Meeting, Anaheim,
CA, March 21-25, 1999; American Chemical Society: Washington,
DC, 1999; NUCL-184.
(19) Zhuang, Z.-P.; Plo¨ssl, K.; Kung, M.-P.; Mu, M.; Jung, H. F. Nucl.
Med. Biol. 1999, 26, 217.
(20) Wong, E.; Fauconnier, T.; Bennett, S.; Valliant, J.; Nguyen, T.; Lau,
F.; Lu, L. F. L.; Pollak, A.; Bell, R. A.; Thornback, J. R. Inorg. Chem.
1997, 36, 5799.
(21) Hansen, L.; Hirota, S.; Xu, X.; Taylor, A. T.; Marzilli, L. G. Inorg.
Chem. 2000, 39, 5731 and references therein.
(22) Tisato, F.; Refosco, F.; Ossola, F.; Bolzati, C.; Bandoli, G.; Transition-
Met. Chem. (London) 1997, 22, 606 and references therein.
(23) Ossola, F.; Tisato, F.; Refosco, F. Inorg. Chim. Acta 2002, 330, 17.
(24) Bolzati, C.; Tisato, F.; Refosco, F.; Bandoli, G.; Domella, A. Inorg.
Chem. 1996, 35, 6221.
(7) (a) Bolzati, C.; Boschi, A.; Uccelli, L.; Malogo, E.; Bandoli, G.; Tisato,
F.; Refosco, F.; Pasqualini, R.; Duatti, A. Inorg. Chem. 1999, 38, 4473.
(b) Bolzati, C.; Boschi, A.; Uccelli, L.; Tisato, F.; Refosco, F.;
Cagnolini, A.; Duatti, A.; Prakash, S.; Bandoli, G.; Vittadini, A. J.
Am. Chem. Soc. 2002, 124 (38), 11468 and references therein.
(8) Hirsch-Kuchma, M.; Nicholson, T.; Davison, A.; Jones, A. G. J. Chem.
Soc., Dalton Trans. 1997, 3189.
(9) Rose, D. J.; Maresca, K. P.; Nicholson, T.; Davison, A.; Jones, A.
G.; Babich, J.; Fischman, A.; Graham, W.; DeBord, J. R. D.; Zubieta,
J. Inorg. Chem. 1998, 37, 2701 and references therein.
(10) (a) Waibei, R.; Alberto, R.; Willude, J.; Finnern, R.; Schibli, R.;
Stichelberger, A.; Egli, A.; Abram, U.; Mach, J. P.; Pluckthern, A.;
Schubiger, P. A. Nat. Biotechnol. 1999, 17, 897. (b) Egli, A.; Alberto,
R.; Tannahill, L.; Schibli, R.; Abram, U.; Schaffland, A.; Waibel, R.;
Tourwe, D.; Jeannin, L.; Iterbeke, K.; Schubiger, P. A. J. Nucl. Med.
1999, 40, 1913. (c) Schibli, R.; LaBelle, R.; Alberto, R.; Garcia-
Garayoa, L.; Ortner, K.; Abram, U.; Schubiger, P. A. Bioconjugate
Chem. 2000, 11, 345. (d) Pak, J. K.; Benny, P.; Spingler, B.; Ortner,
K.; Alberto, R. Chemistry 2003, 9, 2053. (e) Alberto, R.; Schbli, R.;
Angst, D.; Schubiger, P. A.; Abram, U.; Abram, S.; Kaden, T. L. A.
Transition Met. Chem. (London) 1997, 22, 597. (f) Alberto, R.; Schlibi,
R.; Egli, A.; Schubiger, A. P. A. J. Am. Chem. Soc. 1998, 120, 7987.
(g) Alberto, R.; Schlibi, R.; Schubiger, A. P. J. Am. Chem. Soc. 1999,
121, 6076. (h) Amann, A.; Decristoforo, C.; Ott, I.; Wenger, M.; Bader,
D.; Alberto, R.; Putz, G. Nucl. Med. Biol. 2001, 28, 243. (i) Schibli,
R.; Schwartzbach, R.; Alberto, R.; Ortner, K.; Schmalle, H.; Dumas,
C.; Egli, A.; Schubiger, P. A. Bioconjugate Chem. 2002, 13, 750. (j)
Alberto, R.; Ortner, K.; Wheatley, N.; Schibli, R.; Schubiger, A. P. J.
Am. Chem. Soc. 2001, 123, 3135.
(11) (a) Stephenson, K. A.; Zubieta, J.; Banerjee, S. R.; Levadala, M. K.;
Taggart, L.; Ryan, L.; McFarlane, N.; Boreham, D. R.; Maresca, K.
P.; Babich, J. W.; Valliant, J. F. Bioconjugate Chem. 2004, 15, 128.
(b) Banerjee, S. R.; Levadala, M. K.; Lazarova, N.; Wei, L.; Valliant,
J. F.; Stephenson, K. A.; Babich, J. W.; Maresca, K. P.; Zubieta, J.
Inorg. Chem. 2002, 41, 6417. (c) Wei, L.; Banerjee, S. R.; Levadala,
M. K.; Babich, J. W.; Zubieta, J. Inorg. Chem. Commun. 2003, 6,
1099.
(12) Papadopoulos, M.; Nock, B.; Maina, T.; Pirmettis, I.; Raptopoulou,
C.; Tasiopoulos, A.; Troganis, A.; Kabanos, T.; Terzis, A.; Chiotellis,
E. J. Biol. Inorg. Chem. 2001, 6, 159.
(13) Vanbilloen, H. P.; Bormans, G. M.; DeRoo, M. J.; Verbruggen, A.
M. Nucl. Med. Biol. 1996, 22, 325 and references therein.
(14) Rao, T. N.; Adhikesavalu, D.; Camerman, A.; Fritzberg, A. R. J. Am.
Chem. Soc. 1990, 112, 5798.
(15) Meegalla, S.; Plo¨ssl, K.; Kung, M.-P.; Chumpradit, S.; Stevenson, D.
A.; Kushner, S. A.; McElgin, W. T.; Mozley, P. D.; Kung, H. F. J.
Med. Chem. 1997, 40, 9 and references therein.
(16) O’Neill, J. P.; Wilson, S. R.; Katzenellenbogen, J. A. Inorg. Chem.
1994, 33, 319.
(17) (a) Rajagopalan, R.; Grummom, G. D.; Bugaj, J.; Hallemann, L. S.;
Webb, E. G.; Marmion, M. E.; Vanderheyden, J.-L.; Srinivasan, A.
Bioconjugate Chem. 1997, 8, 407. (b) Pollak, A.; Roe, D. G.; Pollack,
C. M.; Lu, L. F.; Thornback, J. R. J. Am. Chem. Soc. 1999, 121, 11593.
(25) Kurti, L.; Papagiannopoulou, D.; Papadopoulos, M.; Pirmettis, I.;
Raptopoulou, C. P.; Terzis, A.; Chiotellis, E.; Harmata, M.; Kuntz,
R. R.; Pandurangi, R. S. Inorg. Chem. 2003, 42, 2960.
(26) Papadopoulos, M.; Pirmettis, I.; Tsoukalas, C.; Nock, B.; Maina, T.;
Raptopoulou, C. P.; Pietzsch, H.-J.; Friebe, M.; Spies, H.; Johannsen,
B.; Chiotellis, E. Inorg. Chim. Acta 1999, 295, 1-8.
(27) Siefert, S.; Gupta, A.; Syhre, R.; Spies, H.; Johannsen, B. Appl. Radiat.
Isot. 2001, 54, 637 and references therein.
(28) Syhre, R.; Seifert, S.; Spies, H.; Gupta, A.; Johannsen, B. Stability
versus reactivity of “3+1” mixed-ligand technetium-99m complexes
in vitro and in vivo. Eur. J. Nucl. Med. 1998, 25 (7), 793-796.
(29) Nock, B.; Maina, T.; Tisato, F.; Papadopoulos, M.; Raptopoulou, C.
P.; Terzis, A.; Chiotellis, E. Inorg. Chem. 2000, 39, 2178.
6446 Inorganic Chemistry, Vol. 43, No. 20, 2004