Maria Contel - Academia.edu (original) (raw)
Papers by Maria Contel
ChemInform, Jun 30, 2009
www.cheminform.wiley-vch.de Catalysis O 0020 Gold(III) Iminophosphorane Complexes as Catalysts in... more www.cheminform.wiley-vch.de Catalysis O 0020 Gold(III) Iminophosphorane Complexes as Catalysts in CC and CO Bond Formations.-Several novel air-and moisture-stable iminophosphorane-Au(III) complexes (I), (II) are prepared. These complexes show catalytic activity comparable to AuCl3 in the addition of methylfuran (III) towards methyl vinyl ketone (IV) and in the intramolecular CO bond formation of various propargylic amides like (VI) and (VIII) to give the corresponding oxazoles. In contrast to AuCl3, however, the reactions can be carried out under air.
Synthetic Communications, Sep 14, 2011
An efficient and high-yield procedure to prepare methyl N-benzoylamino-3-arylacrylates from unsat... more An efficient and high-yield procedure to prepare methyl N-benzoylamino-3-arylacrylates from unsaturated (Z)-2-aryl-4-arylidene-5-(4H)-oxazolones and Hg(OAc) 2 in methanol is described herein. The observed reactivity of mercury(II) acetate here is different to its usual metallating behaviour, since it cleaves the unsaturated oxazolone ring without change of stereochemistry.
Organometallics, Feb 22, 2010
ChemInform, Apr 26, 2012
Reactivity of Unsaturated 5(4H)-Oxazolones with Hg(II) Acetate: Synthesis of Methyl N-Benzoylamin... more Reactivity of Unsaturated 5(4H)-Oxazolones with Hg(II) Acetate: Synthesis of Methyl N-Benzoylamino-3-arylacrylates.-The high-yielding process affords the title compounds without changing the stereochemistry of the substrates. In the case of the electron-activated derivative (Id), no reaction takes place.-(ROIBAN*, G.-D.;
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](Organometallics, 1996
The reaction of the complex [Au(mes)L] (mes) mesityl, L) PPh 3 , AsPh 3) with Ag(OSO 2-CF 3), Ag(... more The reaction of the complex [Au(mes)L] (mes) mesityl, L) PPh 3 , AsPh 3) with Ag(OSO 2-CF 3), Ag(OClO 3), or [Cu(CNMe) 4 ]PF 6 , in molar ratio 2:1, affords trinuclear derivatives [{Au-(µ-mes)L} 2 M]A [M) Ag, L) PPh 3 , A) SO 3 CF 3-(1); L) AsPh 3 , A) ClO 4-(2a), SO 3 CF 3-(2b); M) Cu, A) PF 6-, L) PPh 3 (3), AsPh 3 (4)]. Complexes 1 and 2 react further with various ligands in a 1:1 molar ratio to give the dinuclear compounds [AuAg(µ-mes)-(PPh 3)L]SO 3 CF 3 (L) PPh 3 , tetrahydrothiophene, 2,2′-bipyridine, or SPPh 3) or [AuAg(µmes)(AsPh 3)L]A (L) AsPh 3 , A) SO 3 CF 3-; L) 1 / 2 Ph 2 AsCH 2 AsPh 2 , A) ClO 4-). The structure of [{Au(µ-mes)AsPh 3 } 2 Ag](ClO 4) (2a) has been determined by a single-crystal X-ray diffraction study, which shows an Au-Ag distance of 2.7758(8) Å; the trinuclear species are connected by short Au‚‚‚Au contacts of 3.132 Å to form a chain polymer. Figure 3. Representation of the two-electron three-center Au-C(mesityl)-Ag bond.
Journal of Organometallic Chemistry, 2000
The reaction between PPN[AuCl4] and [Hg(mes)2] gives the anionic complex cis-PPN[Au(mes)2Cl2] (1)... more The reaction between PPN[AuCl4] and [Hg(mes)2] gives the anionic complex cis-PPN[Au(mes)2Cl2] (1) and [Hg(mes)Cl] as side-product. Complex 1 is a precursor to other compounds both neutral and cationic. Removal of one chloride ligand affords the mononuclear neutral complexes cis-[Au(mes)2ClL] (L=PPh3 (2), P{p-tol}3 (3), AsPh3 (4), SPPh3 (5)) by addition of a neutral ligand or, alternatively if no ligand is added,
Journal of Medicinal Chemistry, 2015
New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are d... more New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg 2 Cl 6 2− or PF 6 − respectively, display almost identical IC 50 values in the sub-micromolar range (25−335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspaseindependent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration.
ChemInform, 2005
ABSTRACT For Abstract see ChemInform Abstract in Full Text.
J. Chem. Soc., Dalton Trans., 1994
... Acad. Cienc. Exactas, Fís-Quím. Nat. Zaragoza, 1976, 31, 211 . 17, DH Johnston and DF Shriver... more ... Acad. Cienc. Exactas, Fís-Quím. Nat. Zaragoza, 1976, 31, 211 . 17, DH Johnston and DF Shriver, Inorg. Chem., 1993, 32, 1045 Article CAS . 18, R. Usón, A. Laguna, EJ Fernáandez, A. Mendía and PG Jones, J. Organomet. Chem., 1988, 350, 129 Article CAS . ...
Journal of the American Chemical Society, 2003
Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the ad... more Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(III) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol % with respect to the alkyne). Thus, compounds of the general formula Q[AuRCl(3)], Q[AuR(2)Cl(2)], [AuRCl(2)](2), and [AuR(2)Cl](2) (Q = BzPPh(3)(+), PPN: N(PPh(3))(2)(+) or N(Bu)(4)(+); R = C(6)F(5) or 2,4,6-(CH(3))(3)C(6)H(2)) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C(6)F(5))(2)Cl](2) and phenylacetylene that was followed by variable temperature (1)H, (19)F[(1)H], COSY (19)F[(1)H]-(19)F[(1)H], and (2)H[(1)H] NMR experiments. Compound [Au(C(6)F(5))(2)Cl](2) is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.
Journal of Organometallic Chemistry, 2004
Gold (III) and gold (I) anionic salts mediate the 1, 3-dipolar cycloaddition of N-benzyl-C (2-pyr... more Gold (III) and gold (I) anionic salts mediate the 1, 3-dipolar cycloaddition of N-benzyl-C (2-pyridyl) nitrone (2-PyBN)(1) and methyl acrylate (2)(gold 5–10 mol% with respect to the nitrone) decreasing the reaction time and favouring the formation of the exo (cis) isomer. ...
Inorganic Chemistry, 1997
The reaction of [MeSi{Me(2)SiN(Li)(p-tol)}(3)(Et(2)O)(2)] with SnCl(2) in a 1:1 molar ratio leads... more The reaction of [MeSi{Me(2)SiN(Li)(p-tol)}(3)(Et(2)O)(2)] with SnCl(2) in a 1:1 molar ratio leads the tris(amido)stannate [MeSi{Me(2)SiN(p-tol)}(3)SnLi(Et(2)O)] (1), which further reacts with neutral [AuCl(PPh(3))] and anionic [PPN][AuCl(2)], PPN[AuRCl] (R = C(6)F(5), mes), and chlorogold(I) complexes yielding [Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(PPh(3))] (2) and [PPN][Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(2)] (3) and [Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(R)] (R = C(6)F(5), 4; R = mes, 5), respectively. The reaction of 1 with the dinuclear gold(II) derivative [Au(2)(CH(2)PPh(2)CH(2))(2)Cl(2)] in a 1:2 ratio affords [Au(2)(CH(2)PPh(2)CH(2))(2)(MeSi{Me(2)SiN(p-tol)}(3)Sn)(2)] (6). In a similar way but starting from PPN[Au(C(6)F(5))(3)Cl] and reacting with 1 in a 1:1 ratio, the Au(III) complex [PPN][Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(C(6)F(5))(3)] (7) has been obtained. X-ray crystal structure analyses were performed for compounds 2 and 6, establishing the Sn-Au bonds [d(Au-Sn) = 2.5651(13) and 2.6804(13) Å, respectively). Compound 6 has a nearly linear Sn-Au-Au-Sn array and features the first examples of tin-gold(II) bonds.
Inorganic Chemistry, 1998
Organometallics, 2014
Early−late transition metal TiAu 2 compounds [(η-C 5 H 5) 2 Ti{OC(O)CH 2 PPh 2 AuCl} 2 ] (3) and ... more Early−late transition metal TiAu 2 compounds [(η-C 5 H 5) 2 Ti{OC(O)CH 2 PPh 2 AuCl} 2 ] (3) and new [(η-C 5 H 5) 2 Ti{OC(O)-4-C 6 H 4 PPh 2 AuCl} 2 ] (5) were evaluated as potential anticancer agents in vitro against renal and prostate cancer cell lines. The compounds were significantly more effective than monometallic titanocene dichloride and gold(I) [{HOC(O)RPPh 2 }AuCl] (R = −CH 2 − 6, −4-C 6 H 4 − 7) derivatives in renal cancer cell lines, indicating a synergistic effect of the resulting heterometallic species. The activity on renal cancer cell lines (for 5 in the nanomolar range) was considerably higher than that of cisplatin and highly active titanocene Y. Initial mechanistic studies in Caki-1 cells in vitro coupled with studies of their inhibitory properties on a panel of 35 kinases of oncological interest indicate that these compounds inhibit protein kinases of the AKT and MAPKAPK families with a higher selectivity toward MAPKAPK3 (IC 50 3 = 91 nM, IC 50 5 = 117 nM). The selectivity of the compounds in vitro against renal cancer cell lines when compared to a nontumorigenic human embryonic kidney cell line (HEK-293T) and the favorable preliminary toxicity profile on C57black6 mice indicate that these compounds (especially 5) are excellent candidates for further development as potential renal cancer chemotherapeutics.
Journal of Organometallic Chemistry, 2000
The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4... more The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO)(PPh 3 ) 2 ] [M= Ru (1), Os ], which contain a four-membered cyclometallated ring. A single-crystal X-ray diffraction study of 2 shows the geometry about osmium to be distorted octahedral with the phosphorus atoms in a meridional arrangement. Both complexes react with CO, which displaces one of the triphenylphosphine ligands, the product from 2 being [OsCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. In the case of 1, there is an accompanying migratory insertion of coordinated CO into the Ru C bond to give the five-membered cyclic acyl complex [RuCl(o-C(O)C 6 H 4 P ¹¹¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. Complex 2 reacts with AgSbF 6 in the presence of CO to give [Os(o-C 6 H 4 P ¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 ) 2 ]SbF 6 .
Journal of Organometallic Chemistry
The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4... more The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO)(PPh 3 ) 2 ] [M= Ru (1), Os ], which contain a four-membered cyclometallated ring. A single-crystal X-ray diffraction study of 2 shows the geometry about osmium to be distorted octahedral with the phosphorus atoms in a meridional arrangement. Both complexes react with CO, which displaces one of the triphenylphosphine ligands, the product from 2 being [OsCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. In the case of 1, there is an accompanying migratory insertion of coordinated CO into the Ru C bond to give the five-membered cyclic acyl complex [RuCl(o-C(O)C 6 H 4 P ¹¹¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. Complex 2 reacts with AgSbF 6 in the presence of CO to give [Os(o-C 6 H 4 P ¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 ) 2 ]SbF 6 .
Organometallics, 2014
Early-late transition metal TiAu2 compounds [(η-C5H5)2Ti{OC(O)CH2PPh2AuCl}2] (3) and new [(η-C5H5... more Early-late transition metal TiAu2 compounds [(η-C5H5)2Ti{OC(O)CH2PPh2AuCl}2] (3) and new [(η-C5H5)2Ti{OC(O)-4-C6H4PPh2AuCl}2] (5) were evaluated as potential anticancer agents in vitro against renal and prostate cancer cell lines. The compounds were significantly more effective than monometallic titanocene dichloride and gold(I) [{HOC(O)RPPh2}AuCl] (R = -CH2- 6, -4-C6H4- 7) derivatives in renal cancer cell lines, indicating a synergistic effect of the resulting heterometallic species. The activity on renal cancer cell lines (for 5 in the nanomolar range) was considerably higher than that of cisplatin and highly active titanocene Y. Initial mechanistic studies in Caki-1 cells in vitro coupled with studies of their inhibitory properties on a panel of 35 kinases of oncological interest indicate that these compounds inhibit protein kinases of the AKT and MAPKAPK families with a higher selectivity toward MAPKAPK3 (IC50 3 = 91 nM, IC50 5 = 117 nM). The selectivity of the compounds in vitro against renal cancer cell lines when compared to a nontumorigenic human embryonic kidney cell line (HEK-293T) and the favorable preliminary toxicity profile on C57black6 mice indicate that these compounds (especially 5) are excellent candidates for further development as potential renal cancer chemotherapeutics.
ChemInform, Jun 30, 2009
www.cheminform.wiley-vch.de Catalysis O 0020 Gold(III) Iminophosphorane Complexes as Catalysts in... more www.cheminform.wiley-vch.de Catalysis O 0020 Gold(III) Iminophosphorane Complexes as Catalysts in CC and CO Bond Formations.-Several novel air-and moisture-stable iminophosphorane-Au(III) complexes (I), (II) are prepared. These complexes show catalytic activity comparable to AuCl3 in the addition of methylfuran (III) towards methyl vinyl ketone (IV) and in the intramolecular CO bond formation of various propargylic amides like (VI) and (VIII) to give the corresponding oxazoles. In contrast to AuCl3, however, the reactions can be carried out under air.
Synthetic Communications, Sep 14, 2011
An efficient and high-yield procedure to prepare methyl N-benzoylamino-3-arylacrylates from unsat... more An efficient and high-yield procedure to prepare methyl N-benzoylamino-3-arylacrylates from unsaturated (Z)-2-aryl-4-arylidene-5-(4H)-oxazolones and Hg(OAc) 2 in methanol is described herein. The observed reactivity of mercury(II) acetate here is different to its usual metallating behaviour, since it cleaves the unsaturated oxazolone ring without change of stereochemistry.
Organometallics, Feb 22, 2010
ChemInform, Apr 26, 2012
Reactivity of Unsaturated 5(4H)-Oxazolones with Hg(II) Acetate: Synthesis of Methyl N-Benzoylamin... more Reactivity of Unsaturated 5(4H)-Oxazolones with Hg(II) Acetate: Synthesis of Methyl N-Benzoylamino-3-arylacrylates.-The high-yielding process affords the title compounds without changing the stereochemistry of the substrates. In the case of the electron-activated derivative (Id), no reaction takes place.-(ROIBAN*, G.-D.;
Organometallics, 1996
The reaction of the complex [Au(mes)L] (mes) mesityl, L) PPh 3 , AsPh 3) with Ag(OSO 2-CF 3), Ag(... more The reaction of the complex [Au(mes)L] (mes) mesityl, L) PPh 3 , AsPh 3) with Ag(OSO 2-CF 3), Ag(OClO 3), or [Cu(CNMe) 4 ]PF 6 , in molar ratio 2:1, affords trinuclear derivatives [{Au-(µ-mes)L} 2 M]A [M) Ag, L) PPh 3 , A) SO 3 CF 3-(1); L) AsPh 3 , A) ClO 4-(2a), SO 3 CF 3-(2b); M) Cu, A) PF 6-, L) PPh 3 (3), AsPh 3 (4)]. Complexes 1 and 2 react further with various ligands in a 1:1 molar ratio to give the dinuclear compounds [AuAg(µ-mes)-(PPh 3)L]SO 3 CF 3 (L) PPh 3 , tetrahydrothiophene, 2,2′-bipyridine, or SPPh 3) or [AuAg(µmes)(AsPh 3)L]A (L) AsPh 3 , A) SO 3 CF 3-; L) 1 / 2 Ph 2 AsCH 2 AsPh 2 , A) ClO 4-). The structure of [{Au(µ-mes)AsPh 3 } 2 Ag](ClO 4) (2a) has been determined by a single-crystal X-ray diffraction study, which shows an Au-Ag distance of 2.7758(8) Å; the trinuclear species are connected by short Au‚‚‚Au contacts of 3.132 Å to form a chain polymer. Figure 3. Representation of the two-electron three-center Au-C(mesityl)-Ag bond.
Journal of Organometallic Chemistry, 2000
The reaction between PPN[AuCl4] and [Hg(mes)2] gives the anionic complex cis-PPN[Au(mes)2Cl2] (1)... more The reaction between PPN[AuCl4] and [Hg(mes)2] gives the anionic complex cis-PPN[Au(mes)2Cl2] (1) and [Hg(mes)Cl] as side-product. Complex 1 is a precursor to other compounds both neutral and cationic. Removal of one chloride ligand affords the mononuclear neutral complexes cis-[Au(mes)2ClL] (L=PPh3 (2), P{p-tol}3 (3), AsPh3 (4), SPPh3 (5)) by addition of a neutral ligand or, alternatively if no ligand is added,
Journal of Medicinal Chemistry, 2015
New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are d... more New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg 2 Cl 6 2− or PF 6 − respectively, display almost identical IC 50 values in the sub-micromolar range (25−335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspaseindependent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration.
ChemInform, 2005
ABSTRACT For Abstract see ChemInform Abstract in Full Text.
J. Chem. Soc., Dalton Trans., 1994
... Acad. Cienc. Exactas, Fís-Quím. Nat. Zaragoza, 1976, 31, 211 . 17, DH Johnston and DF Shriver... more ... Acad. Cienc. Exactas, Fís-Quím. Nat. Zaragoza, 1976, 31, 211 . 17, DH Johnston and DF Shriver, Inorg. Chem., 1993, 32, 1045 Article CAS . 18, R. Usón, A. Laguna, EJ Fernáandez, A. Mendía and PG Jones, J. Organomet. Chem., 1988, 350, 129 Article CAS . ...
Journal of the American Chemical Society, 2003
Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the ad... more Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(III) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol % with respect to the alkyne). Thus, compounds of the general formula Q[AuRCl(3)], Q[AuR(2)Cl(2)], [AuRCl(2)](2), and [AuR(2)Cl](2) (Q = BzPPh(3)(+), PPN: N(PPh(3))(2)(+) or N(Bu)(4)(+); R = C(6)F(5) or 2,4,6-(CH(3))(3)C(6)H(2)) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C(6)F(5))(2)Cl](2) and phenylacetylene that was followed by variable temperature (1)H, (19)F[(1)H], COSY (19)F[(1)H]-(19)F[(1)H], and (2)H[(1)H] NMR experiments. Compound [Au(C(6)F(5))(2)Cl](2) is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.
Journal of Organometallic Chemistry, 2004
Gold (III) and gold (I) anionic salts mediate the 1, 3-dipolar cycloaddition of N-benzyl-C (2-pyr... more Gold (III) and gold (I) anionic salts mediate the 1, 3-dipolar cycloaddition of N-benzyl-C (2-pyridyl) nitrone (2-PyBN)(1) and methyl acrylate (2)(gold 5–10 mol% with respect to the nitrone) decreasing the reaction time and favouring the formation of the exo (cis) isomer. ...
Inorganic Chemistry, 1997
The reaction of [MeSi{Me(2)SiN(Li)(p-tol)}(3)(Et(2)O)(2)] with SnCl(2) in a 1:1 molar ratio leads... more The reaction of [MeSi{Me(2)SiN(Li)(p-tol)}(3)(Et(2)O)(2)] with SnCl(2) in a 1:1 molar ratio leads the tris(amido)stannate [MeSi{Me(2)SiN(p-tol)}(3)SnLi(Et(2)O)] (1), which further reacts with neutral [AuCl(PPh(3))] and anionic [PPN][AuCl(2)], PPN[AuRCl] (R = C(6)F(5), mes), and chlorogold(I) complexes yielding [Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(PPh(3))] (2) and [PPN][Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(2)] (3) and [Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(R)] (R = C(6)F(5), 4; R = mes, 5), respectively. The reaction of 1 with the dinuclear gold(II) derivative [Au(2)(CH(2)PPh(2)CH(2))(2)Cl(2)] in a 1:2 ratio affords [Au(2)(CH(2)PPh(2)CH(2))(2)(MeSi{Me(2)SiN(p-tol)}(3)Sn)(2)] (6). In a similar way but starting from PPN[Au(C(6)F(5))(3)Cl] and reacting with 1 in a 1:1 ratio, the Au(III) complex [PPN][Au(MeSi{Me(2)SiN(p-tol)}(3)Sn)(C(6)F(5))(3)] (7) has been obtained. X-ray crystal structure analyses were performed for compounds 2 and 6, establishing the Sn-Au bonds [d(Au-Sn) = 2.5651(13) and 2.6804(13) Å, respectively). Compound 6 has a nearly linear Sn-Au-Au-Sn array and features the first examples of tin-gold(II) bonds.
Inorganic Chemistry, 1998
Organometallics, 2014
Early−late transition metal TiAu 2 compounds [(η-C 5 H 5) 2 Ti{OC(O)CH 2 PPh 2 AuCl} 2 ] (3) and ... more Early−late transition metal TiAu 2 compounds [(η-C 5 H 5) 2 Ti{OC(O)CH 2 PPh 2 AuCl} 2 ] (3) and new [(η-C 5 H 5) 2 Ti{OC(O)-4-C 6 H 4 PPh 2 AuCl} 2 ] (5) were evaluated as potential anticancer agents in vitro against renal and prostate cancer cell lines. The compounds were significantly more effective than monometallic titanocene dichloride and gold(I) [{HOC(O)RPPh 2 }AuCl] (R = −CH 2 − 6, −4-C 6 H 4 − 7) derivatives in renal cancer cell lines, indicating a synergistic effect of the resulting heterometallic species. The activity on renal cancer cell lines (for 5 in the nanomolar range) was considerably higher than that of cisplatin and highly active titanocene Y. Initial mechanistic studies in Caki-1 cells in vitro coupled with studies of their inhibitory properties on a panel of 35 kinases of oncological interest indicate that these compounds inhibit protein kinases of the AKT and MAPKAPK families with a higher selectivity toward MAPKAPK3 (IC 50 3 = 91 nM, IC 50 5 = 117 nM). The selectivity of the compounds in vitro against renal cancer cell lines when compared to a nontumorigenic human embryonic kidney cell line (HEK-293T) and the favorable preliminary toxicity profile on C57black6 mice indicate that these compounds (especially 5) are excellent candidates for further development as potential renal cancer chemotherapeutics.
Journal of Organometallic Chemistry, 2000
The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4... more The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO)(PPh 3 ) 2 ] [M= Ru (1), Os ], which contain a four-membered cyclometallated ring. A single-crystal X-ray diffraction study of 2 shows the geometry about osmium to be distorted octahedral with the phosphorus atoms in a meridional arrangement. Both complexes react with CO, which displaces one of the triphenylphosphine ligands, the product from 2 being [OsCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. In the case of 1, there is an accompanying migratory insertion of coordinated CO into the Ru C bond to give the five-membered cyclic acyl complex [RuCl(o-C(O)C 6 H 4 P ¹¹¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. Complex 2 reacts with AgSbF 6 in the presence of CO to give [Os(o-C 6 H 4 P ¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 ) 2 ]SbF 6 .
Journal of Organometallic Chemistry
The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4... more The reaction between H 4 PPh 2 ) 2 ] and [MHCl(CO)(PPh 3 ) 3 ] gives the complexes [MCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO)(PPh 3 ) 2 ] [M= Ru (1), Os ], which contain a four-membered cyclometallated ring. A single-crystal X-ray diffraction study of 2 shows the geometry about osmium to be distorted octahedral with the phosphorus atoms in a meridional arrangement. Both complexes react with CO, which displaces one of the triphenylphosphine ligands, the product from 2 being [OsCl(o-C 6 H 4 P ¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. In the case of 1, there is an accompanying migratory insertion of coordinated CO into the Ru C bond to give the five-membered cyclic acyl complex [RuCl(o-C(O)C 6 H 4 P ¹¹¹¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 )]. Complex 2 reacts with AgSbF 6 in the presence of CO to give [Os(o-C 6 H 4 P ¹¹¹¹¹º Ph 2 )(CO) 2 (PPh 3 ) 2 ]SbF 6 .
Organometallics, 2014
Early-late transition metal TiAu2 compounds [(η-C5H5)2Ti{OC(O)CH2PPh2AuCl}2] (3) and new [(η-C5H5... more Early-late transition metal TiAu2 compounds [(η-C5H5)2Ti{OC(O)CH2PPh2AuCl}2] (3) and new [(η-C5H5)2Ti{OC(O)-4-C6H4PPh2AuCl}2] (5) were evaluated as potential anticancer agents in vitro against renal and prostate cancer cell lines. The compounds were significantly more effective than monometallic titanocene dichloride and gold(I) [{HOC(O)RPPh2}AuCl] (R = -CH2- 6, -4-C6H4- 7) derivatives in renal cancer cell lines, indicating a synergistic effect of the resulting heterometallic species. The activity on renal cancer cell lines (for 5 in the nanomolar range) was considerably higher than that of cisplatin and highly active titanocene Y. Initial mechanistic studies in Caki-1 cells in vitro coupled with studies of their inhibitory properties on a panel of 35 kinases of oncological interest indicate that these compounds inhibit protein kinases of the AKT and MAPKAPK families with a higher selectivity toward MAPKAPK3 (IC50 3 = 91 nM, IC50 5 = 117 nM). The selectivity of the compounds in vitro against renal cancer cell lines when compared to a nontumorigenic human embryonic kidney cell line (HEK-293T) and the favorable preliminary toxicity profile on C57black6 mice indicate that these compounds (especially 5) are excellent candidates for further development as potential renal cancer chemotherapeutics.