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Chemistry of the D-Block Elements Chemistry of the D-Block Elements Chemistry of the d-Block Elements History: Louis Nicolas Vauquelin 16. Mai 1763 – 14. Nov. 1829 Leopold Gmelin 2. Aug. 1788 – 13. Apr. 1853 Chemistry of the d-Block Elements History: H3N NH3 Cl Cl Pd Pd NH H3N 3 Cl Cl Louis Nicolas Vauquelin 1813 CN NC CN CoIII NC CN Gmelin 1822 NC 1 Chemistry of the d-Block Elements History: 1844: Peyrone’s Chloride 1844: Reiset [PtCl2(NH3)2] -- note! same formula! -- [PtCl2(NH3)2] ! (isomers are super-important in chemistry!) Chemistry of the d-Block Elements cis- and trans- Platinum Isomers: Serendipity in Chemistry Cisplatin was approved by the FDA for the treatment of genitourinary tumors in 1978. Since then, Michigan State has collected over $160 million in royalties from cisplatin and a related drug, carboplatin, which Prof. Barnett Rosenberg, MSU was approved by the FDA in 1989 (Prof. S.J. Lippard, MIT) for the treatment of ovarian cancers. "Testicular cancer went from a disease that normally killed about 80% of the patients, to one which is close to 95% curable. This is Newest generation: probably the most exciting development in the treatment of cancers that we have had in the past 20 years. It is now the O treatment of first choice in ovarian, bladder, and osteogenic sarcoma [bone] cancers as well." O NH3 —Barnett Rosenberg, who led the research group that discovered Pt cisplatin, commenting on the impact of cisplatin in cancer chemotherapy O NH3 O carboplatin 2 Chemistry of the d-Block Elements Cisplatin acts by cross-linking DNA in several different ways, making it impossible for rapidly dividing cells to duplicate their DNA for mitosis. The damaged DNA sets off DNA repair mechanisms, which activate apoptosis when repair proves impossible. The trans-isomer does not have this pharmacological effect. B. Rosenberg et al. in Nature 1965, 205, 698 Stephen J. Lippard et al. in Nature (1999), 399, 708 - 712 Basis for recognition of cisplatin-modified DNA by high-mobility-group proteins SUMMARY: The anticancer activity of cis -diamminedichloroplatinum(II) (cisplatin) arises from its ability to damage DNA, with the major adducts formed being intrastrand Barnett Rosenberg, MSU (1926 - ) d(GpG) and d(ApG) Chemistry of the d-Block Elements Cisplatin acts by crosslinking DNA in several different ways, making it impossible for rapidly dividing cells to duplicate their DNA for mitosis. The damaged DNA sets off DNA repair mechanisms, which activate apoptosis when repair proves impossible. The trans isomer does not have this pharmacological effect. B. Rosenberg et al. in Nature 1965, 205, 698 Stephen J. Lippard et al. in Nature (1999), 399, 708 - 712 Basis for recognition of cisplatin-modified DNA by high-mobility-group proteins SUMMARY: The anticancer activity of cis -diamminedichloroplatinum(II) (cisplatin) arises from its ability to damage DNA, with the major adducts formed being intrastrand Stephen J. Lippard, MIT (??? - ) d(GpG) and d(ApG) 3 Chemistry of the d-Block Elements Cisplatin acts by crosslinking DNA in several different ways, making it impossible for rapidly dividing cells to duplicate their DNA for mitosis. The damaged DNA sets off DNA repair mechanisms, which activate apoptosis when repair proves impossible. The trans isomer does not have this pharmacological effect. B. Rosenberg et al. in Nature 1965, 205, 698 Stephen J. Lippard et al. in Nature (1999), 399, 708 - 712 Basis for recognition of cisplatin-modified DNA by high-mobility-group proteins SUMMARY: The anticancer activity of cis -diamminedichloroplatinum(II) (cisplatin) arises from its ability to damage DNA, with the major adducts formed being intrastrand d(GpG) and d(ApG) Chemistry of the d-Block Elements Another success story at the HEART of coordination chemistry: CardioLite "Davison realized that fundamental coordination chemistry would shed light on the chemical characteristics of the element technetium and that these basic chemical characteristics could be translated into the rational design of new radiopharmaceuticals," Orvig notes in the article. He calls Davison "one of the fathers of medicinal inorganic chemistry.“ Prof. Chris Orvig, University of British Columbia taken from SNM advancing molecular imaging Alan Davison, MIT (??? - ) 4 Chemistry of the d-Block Elements Another success story at the HEART of coordination chemistry: Cardiolite Chemistry of the d-Block Elements The d - Block Elements http://www.chemsoc.org/viselements/pages/pertable_fla.htm 5 Chemistry of the d-Block Elements The d - Block Elements…my personal favorites Chemistry of the d-Block Elements The d - Block Elements…my personal favorites Prof. Karl Wieghardt Max-Planck-Institute for Bioinorganic Chemistry Muelheim/Germany 6 Chemistry of the d-Block Elements The Werner & Jørgensen Controversy Sophus Mads Jørgensen 1837 – 1914 Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry “Dot” Representation: Pentachlorophosphorous PCl5 PCl3 •Cl2 Copper(II) Sulfate Pentahydrate CuSO4 •5H2O Copper(II) Acetate Hydrate Cu(CH3COO)2 •H2O Hex(a)ammin Cobalt(III) Chloride CoCl3 •6NH3 7 Chemistry of the d-Block Elements Alfred Werner Seite 111 des 17-jährigen(!) Alfred Werner‘s „Einleitung in die Chemie“ (1883 – 1884) über die Formulierung des PCl5 als molecular compound PCl3 • Cl2 Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry Copper(II) Acetate Hydrate Cu(CH3COO)2 •H2O Hex(a)ammin Cobalt(III) Chloride CoCl3 •6NH3 8 Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry Hex(a)ammin Cobalt(III) Chloride CoCl3 •6NH3 Prefix Color Complex III • luteo yellow Co Cl3 6NH3 III • purpureo red Co Cl3 5NH3 III • praseo green Co Cl3 4NH3 III • violeo violet Co Cl3 4NH3 Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry Alfred Werner‘s Kollektion (8000+ Komplexe!) & die „Katakomben“ an der Universität Zürich 9 Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry Jørgensen Werner NH3—Cl Co—NH3—Cl [Co(NH3)6]Cl3 NH3—NH3—NH3—NH3—Cl Cl Co—NH3—Cl [Co(NH3)5Cl]Cl2 NH3—NH3—NH3—NH3—Cl Cl Co—Cl 2 [Co(NH3)4(Cl)2]Cl i NH3—NH3—NH3—NH3—Cl s o m e r Cl s Co—Cl ! [Co(NH3)4(Cl)2]Cl NH3—NH3—NH3—Cl Chemistry of the d -Block Elements Alfred Werner – Founder of Coordination Chemistry 10 Chemistry of the d-Block Elements Alfred Werner – Leitfähigkeit (Kohlrausch’s Prinzip, Konstitution) Alfred Werner & Arturo Miolati (1893 – 1896) Chemistry of the d-Block Elements Alfred Werner – Isomere (Konfiguration) 11 Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry Chemistry of the d-Block Elements Alfred Werner – Founder of Coordination Chemistry 12 Chemistry of the d-Block Elements A Sidenote: Serendipity in Chemistry Cisplatin was approved by the FDA for the treatment of genitourinary tumors in 1978. Since then, Michigan State has collected over $160 million in royalties from cisplatin and a related drug, carboplatin, which Prof. Barnett Rosenberg, MSU was approved by the FDA in 1989 (Prof. S.J. Lippard, MIT) for the treatment of ovarian cancers. "Testicular cancer went from a disease that normally killed about 80% of the patients, to one which is close to 95% curable. This is probably the most exciting development in the treatment of cancers that we have had in the past 20 years. It is now the O treatment of first choice in ovarian, bladder, and osteogenic sarcoma [bone] cancers as well." O NH3 —Barnett Rosenberg, who led the research group that discovered Pt cisplatin, commenting on the impact of cisplatin in cancer chemotherapy O NH3 O carboplatin Chemistry of the d-Block Elements First non-carbon containing chiral compound: Hexol [(Co ((OH)2Co(NH3)4)3](SO4)3, resolved in 1914 with (+)-bromocamphorsulphonate O O 6+ Br S NH3 O O H 3N NH3 Co definitive proof of NH3 HO H NH3 Alfred Werner’s H 3N O OH octahedron model Co Co H 3N O -> Synthesis of H OH NH HO optically active 3 NH Co 3 complexes! H 3N NH3 H 3N 13 Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature 14 Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature 15 Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature 16 Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature 17 Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature 18 Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature l oo IUPAC Rules for complex formula: I ks w aw (B ou r) ld k (C u w l s ar • Coordination complex in square brackets, )( e d… I)… charge superscripted III − II − [Cr (NCO)4(NH3)2] [Pt BrClI(NO2)(NH3)] IV [Pt BrClI(NO2)(py)(NH3)] • Central atom in front of ligands abbrev: C5H5N • Anionic in front of neutral ligands • Multiple atoms & abbrev. ligands in round brackets • Oxidation number superscripted @ central atom Chemistry of the d-Block Elements Coordination Chemistry - Nomenclature IUPAC Rules for complex name: Main Difference: ligands first, followed by central atom strictly follow alphabetical order Dichloro(thiourea)(triphenylphosphine)platinum(II) [PtCl2(py)(NH3)] Amminedichloro(pyridine)platinum(II) • Ligands in alphabetical order in front of central atom/ion Specification of oxidation number (Roman
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