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  • 1
    ISSN: 0044-2313
    Keywords: Dithiolato metal complexes ; pentacarbonyl-rhenium ; triphosphinegold ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometallic Lewis Acids. L. Addition of Pentacarbonylrhenium and Triphenylphosphinegold Cations to Anionic Dithiolato Metal Complexes as S-NucleophilesThe organometallic Lewis Acids Ph3PAuNO3 (1) and (CO)5ReFBF3 (2) react with the dithiolato metal complexes (Bu4N)2[M(mnt)2] (mnt = maleonitrildithiolato, M = Ni, Cu, Pt, Zn) and (Bu4N)2[Zn(dmit)2] (dmit = dimercaptoisotrithiono) to give the complexes (Ph3PAu)2mnt (3), (Bu4N)[Ph3PAu(mnt)] (4), (Ph3PAu)2Pt(mnt)2 (5), (Ph3PAu)2dmit (10) and [(CO)5Re]2Ni(mnt)2 (6), (Bu4N){[(CO)5Re]M(mnt)2} (M = Ni, Pt, 7, 8), [(CO)5Re]2(mnt)2 (9) and [(CO)5Re]2Ni(dmit)2 (11), respectively. The compounds 3, 4 and 5 have been characterized by x-ray structural analysis. In 4 the chelate ligand is symmetrically coordinated to the AuI atom. Weak Au—Au (dAu—Au = 309 pm) interactions lead to the formation of chains in the crystal of 3. The trans-anti configuration in 5 can also be assumed for the complexes 6 and 11 for sterical reasons. Compound 1 reacts with K2[M(dto)2] (dto = dithiooxalato, M = Pd, Pt) to give the expected bis(triphenylphosphinegold) adducts 12 and 13. Complex 2, however, affords with dithiooxalato metal dianions the compound [(CO)5Re]2(dto)2 (14) as final product. (Ph3PAu)2dto (15) is obtained by reaction of 1 with K2dto. [(CO)5Re]2FeNO(dto)2 (16) can be isolated as an unstable adduct from the reaction of 2 with [Fe(NO)(dto)2]2- Re(CO)5+ and Ph3PAu+ can be added to the bridging S atoms of [(ON)2Fe(μ-S)2Fe(NO)2]2- to give 17 and 18
    Notes: Die „Metallorganischen Lewis-Säuren“ Ph3PAuNO3 (1) und (CO)5ReFBF3 (2) setzen sich mit den Dithiolato-Metallkomplexen (Bu4N)2[M(mnt)2] (mnt = maleonitrildithiolato, M = Ni, Cu, Pt, Zn) und (Bu4N)2[Zn(dmit)2] (dmit = dimercaptoisotrithiono) zu den Komplexen (Ph3PAu)2mnt (3), (Bu4N)[Ph3PAu(mnt)] (4), (Ph3PAu)2Pt(mnt)2 (5) und (Ph3PAu)2dmit (10) bzw. [(CO)5Re]2Ni(mnt)2 (6), (Bu4N){[(CO)5Re]M(mnt)2} (M = Ni, Pt, 7, 8), [(CO)5Re]2(mnt)2 (9) und [(CO)5Re]2Ni(dmit)2 (11) um. Die Strukturen von 3, 4 und 5 wurden röntgenographisch bestimmt. In 4 ist der Chelatligand symmetrisch an das AuI-Atom gebunden. Im Kristall von 3 entstehen durch schwache Au—Au-Wechselwirkungen Ketten (dAu—Au = 309 pm). Die trans-anti-Konfiguration im Komplex 5 wird aus sterischen Gründen auch für die analogen Komplexe 6 und 11 angenommen. Während 1 mit K2[M(dto)2] (dto = dithiooxalato, M = Pd, Pt) die erwarteten Bis(triphenylphosphangold)-Addukte 12 und 13 bildet, ergibt 2 [(CO)5Re]2 (dto)2 (14) als stabiles Endprodukt. Das Triphenylphosphangold-Analogon 15 erhält man durch Reaktion von 1 mit K2dto. [(CO)5Re]2FeNO(dto)2 (16) kann als primäres Produkt der Reaktion von 2 mit [Fe(NO)(dto)2]2- isoliert werden. Re(CO)5+ und Ph3PAu+ können an die verbrückenden S-Atome von [(ON)2Fe(μ-S)2Fe(NO)2]2- unter Bildung von 17 und 18 addiert werden.
    Additional Material: 7 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: Cyclopentadienyl nitrosyl molybdenum complexes ; α-aminocarboxylate ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes of Biologically Important Ligands. XC [1]. Chiral Cyclopentadienyl-Nitrosyl-Molybdenum Complexes of α-Amino Carboxylates: (η5-C5R5)(ON)(I)Mo(α-aminocarboxylate) (R = H, Me)The reactions of [(η5-C5H5)Mo(NO)I2]2 with glycinate, D-phenylglycinate, L-prolinate and L-azetidine-2-carboxylate give the chiral chelate complexes (η5-C5H5)(ON)(I)Mo(η-aminocarboxylate) as mixtures of isomers. The x-ray diffraction of a crystal of shows trans configuration of the amino acid and nitrosyl donors in a tetragonal pyramid.
    Notes: Die iodoverbrückten Komplexe [(η5-C5H5)Mo(NO)I2]2 setzen sich mit Glycinat, D-Phenylglycinat, L-Prolinat und L-Azetidin-2-carboxylat zu den chiralen Chelat-Komplexen (η5-C5H5)(ON)(I)Mo(α-Aminocarboxylat) um, die als Mischung von Isomeren entstehen. Die Röntgenstrukturanalyse eines Kristalls von zeigt die trans-Konfiguration der Amino- und Nitrosyl-Liganden in einer tetragonalen Pyramide.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Rhodium ; ruthenium ; iridium ; palladium ; proline ; amide complexes ; proline methylester complexes ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes of Biologically Important Ligands. XCV. η5-Pentamethylcyclopentadienyl Rhodium, Iridium, η6- Benzene Ruthenium, and Phosphine Palladium Complexes of Proline Methylester and Proline AmideProline methylester (L1) and proline amide (L2) give with the chloro bridged complexes [(η5 -C5Me5)MCl2]2 (M = Rh, Ir), [(η6 -benzene)RuCl2]2 and [Et3PPdCl2]2 N and N,O coordinated compounds: (η5 -C5Me5)M(Cl2)L1 (1, 2 M = Rh, Ir), [(η5-C5Me5) Rh(Cl)(L2)]+Cl- (5), [(η6- C6Me6) Ru(Cl)(L2)]+Cl- (6), [(η6-p-cymene)Ru(Cl)(L2)]+Cl- (7), [(eta;5-C5Me5)M(Cl)(L2-H+)] (9, 10 M = Rh, Ir), (Et3P)Pd(Cl)2L1 (3), and [(Et3P)Pd(Cl)(L2)]+Cl- (8). The NMR spectra indicate that for 5 and 6 only one diastereoisomer is formed. The complexes 1, 2, 3 and 5 were characterized by X-ray diffraction.
    Notes: Prolinmethylester (L1) und Prolinamid (L2) bilden mit den chlorverbrückten Komplexen [(η5-C5Me5)MCl2]2 (M = Rh, Ir), [(η6-p-Cymol)RuCl2]2 und [Et3PPdCl2]2 Verbindungen mit N- und N,O-Koordination: (η5-C5Me5)M(Cl2)L1 (1, 2 M = Rh, Ir), [(η5-C5Me5) Rh(Cl) (L2)]+Cl- (5), [(η6- C6Me6)Ru(Cl) (L2)]+Cl- (6), [(η6-p- Cymol)Ru(Cl)(L2)]+Cl- (7), [(η5- C5Me5)M(Cl)(L2-H+)] (9, 10 M = Rh, Ir), (Et3P)Pd(Cl)2L1 (3) und [(Et3P)Pd(Cl)(L2)]+Cl- (8). Die NMR Spektren weisen darauf hin, daß von 5 und 6 jeweils nur ein Diastereoisomeres entsteht. Die Komplexe 1, 2, 3 und 5 wurden durch Röntgenstrukturanalyse charakterisiert.
    Additional Material: 4 Ill.
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