Craig M. Anderson

Oxidative addition of aryl–halogen bonds to platinum(II) and the structure of a complex formed by aryl–fluoride oxidative addition

The complexes [PtMe2(Me2NCH2CH2NCHAr)] react by oxidative addition of the aryl–halogen bond when Ar = 2-BrC6H4, 2-CIC6H4, or C6F5 but by ortho-metallation when Ar = 2-FC6H4 or C6H5, and in the case where Ar = C6F5, the oxidative addition product adds acetone across the imine bond and the complex formed has been characterized crystallographically as a hydrogen-bonded dimer; the reactivity to oxidative addition can be correlated with the C–X bond energy.

Hetero-multinuclear Ruthenium(III)/Platinum(II) Complexes That Potentially Exhibit Both Antimetastatic and Antineoplastic Properties

Hetero-multinuclear, platinum/ruthenium species were synthesized and tested for their effect on the motility of A549 (nonsmall cell lung) and MDA-MB-231 (breast) cancer cells and for their ability to inhibit DNA mobility using gel electrophoresis. It was found that the Ru(2)Pt trinuclear species [Na(2)]{[Ru(III)Cl(4)(DMSO-S)(-μ-pyz)](2)Pt(II)Cl(2)}, AH197, was much more efficient at inhibiting cell motility than [C(3)N(2)H(5)][Ru(III)Cl(4)(DMSO-S)(C(3)N(2)H(4))], NAMI-A, while the dinuclear RuPt species [K][Ru(III)Cl(4)(DMSO-S)(-μ-pyz)Pt(II)(DMSO-S)Cl(2)], IT127, was slightly better than NAMI-A. However, the dinuclear species retarded the electrophoretic mobility of DNA greater than both the trinuclear complex and cisplatin. The metal complexes and their respective BSA protein/metal adducts were studied by X-ray absorption spectroscopy. The spectra led to the conclusion that BSA donor atoms have substituted for the chloride ligands and perhaps the DMSO ligands.

Oxidative addition of alkyl halides to chiral cyclometallated platinum(II) complexes with thienyl imines. X-ray crystal structure of [PtMe{3-((S)-PhCHMeNCH)C4H2S}SMe2]

Abstract The reaction of [Pt 2 Me 4 (μ-SMe 2 ) 2 ] with ligand 3-(( S )-PhCHMeNCH)C 4 H 3 S ( 1 ) produced the chiral cyclometallated compound [PtMe{3-(( S )-PhCHMeNCH)C 4 H 2 S}SMe 2 ] ( 2 ) which was characterized structurally. The reactions of 2 with phosphines gave compounds [PtMe{3-(( S )-PhCHMeNCH)C 4 H 2 S}L] (L=PPh 3 ( 3 ), P(2-MeC 6 H 4 ) 3 ( 4 ), Ph 2 PCH 2 CH 2 PPh 2 ( 5 )). The oxidative addition of methyl iodide to compounds 2 and 3 gave two diastereoisomers each of compounds [PtMe 2 I{3-(( S )-PhCHMeNCH)C 4 H 2 S}L] (L=SMe 2 ( 6a / 6a′ ), PPh 3 ( 7a / 7a′ )) in a ratio 2.1:1 and 2.4:1, respectively. Subsequent isomerization gave, in each case, a new pair of diastereoisomers. Compounds 4 and 5 failed to react with methyl iodide, while platinum(II) compounds [PtX{3-(( S )-PhCHMeNCH)C 4 H 2 S}PPh 3 ] (X=I ( 8 ), Br ( 9 )) were obtained in the reactions of 3 with ethyl iodide or benzylbromide.

Stereoselective oxidative addition of methyl iodide to chiral cyclometallated platinum(II) compounds derived from (R)-(+)-1-(1-naphthylethylamine). Crystal structure of [PtMe{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3]

Abstract The reaction of 3-(R)-(C10H7)CHMeNCHC4H3S (2a) with [Pt2Me4(μ-SMe2)2] in acetone gave the new chiral cyclometallated platinum(II) compound [PtMe{3-(R)-(C10H7)CHMeNCHC4H2S}SMe2] (3a). Addition of PPh3 produced compound [PtMe{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3] (4a) which was characterized by X-ray diffraction methods. While oxidative addition of methyl iodide to 3a gave two pairs of diastereomers, the analogous reaction for 4a produced only one diastereomer of the platinum(IV) compound [PtMe2I{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3] (7a). Subsequent isomerization of the resulting platinum(IV) compound gave a new pair of diastereomers in relative amounts 90 and 10%. Analogous proportions of final diastereomers were obtained for the oxidative addition of methyl iodide to the new chiral compounds [PtMe{3-(R)-(C10H7)CHMeNCHAr}PPh3] (Ar=C6H4 (4b), 2-FC6H3 (4c), 2-CF3C6H3 (4d)). The reaction of [Pt2Me4(μ-SMe2)2] with imines (R)-(C10H7)CHMeNCH(2-BrC6H4) (2e) and (R)-(C10H7)CHMeNCH(2,6-Cl2C6H3) (2f) produced intramolecular oxidative addition to yield platinum(IV) compounds with some degree of stereoselectivity.

Synthesis and characterization of water-soluble, heteronuclear ruthenium(III)/ferrocene complexes and their interactions with biomolecules

The reaction of Na[RuCl4(SO(CH3)2)2], 1, with one equivalent of FcCONHCH2C6H4N (Fc=FeC10H9), L1, FcCOOCH2CH2C3H3N2, L2, FcCOOC6H4N, L3, afforded the dinuclear species, Na[FcCONHCH2C6H4N[RuCl4(SO(CH3)2)]], RuL1, Na[FcCOOCH2CH2C3H3N2[RuCl4(SO(CH3)2)]], RuL2, Na[FcCOOC6H4N(RuCl4(SO(CH3)2))], RuL3, respectively, yielding, in each case, a ferrocene moiety bridged to a ruthenium center. The complexes were characterized by NMR, IR, and XRD (X-ray diffraction). The sulfoxide ligands are bonded to the metal through the sulfur atom. The complexes were evaluated for their biological activity with pBluescript DNA plasmid, and the protein BSA (bovine serum albumin). These reactions were monitored by XAS (X-ray absorption spectroscopy), EXAFS (extended X-ray Absorption Fine Structure), NMR, UV/visible, emission spectroscopy, and gel electrophoresis. Donor atoms from the biomolecules substitute for the chloride ligands in the parent complexes.

Poly[μ(3)-chlorido-μ(2)-chloridodichlorido(μ-dimethyl sulfoxide-κO:S)(dimethyl sulfoxide-κO)(μ-pyrimidine-κN:N')-ruthenium(III)sodium].

The title complex, [NaRuCl4(C4H4N2)(C2H6OS)2]n, is the sodium salt of monoanionic octahedral [RuIIICl4(pyrimidine)(DMSO)]− in which the sulfur-bound dimethyl sulfoxide (DMSO) and pyrimidine ligand are oriented trans to one another on the RuIII atom. The average of the four Ru—Cl bond lengths is 2.355 (15) Å, and the Ru—S and Ru—N bond lengths are 2.2853 (3) and 2.1165 (11) Å, respectively. The complex forms a chain, with a six-coordinate sodium ion bridging the ruthenium(III) units. The sodium cation is coordinated by cis-chloride ligands on ruthenium [Na—Cl = 2.9576 (7) and 2.6988 (7) Å], chloride and DMSO ligands from the ruthenium complexes related by inversion [Na—Cl and Na—O = 2.8888 (7) and 2.2623 (12) Å, respectively], a nitrogen ligand from the pyrimidine of the tetrachloridoruthenium(III) complex related by the twofold rotation axis [Na—N = 2.5224 (14) Å] and an oxygen-bound DMSO [Na—O = 2.3165 (12) Å].