Heteronukleare Komplexverbindungen mit Metall?Metall-Bindungen. VIII. Neue heterodinukleare Komplexe mit Bindungen zwischen Kupfer(I) und Mangan(-I), Eisen(-I) oder Cobalt(-I) (original) (raw)
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Zeitschrift für Naturforschung B, 2005
Reactions of L-tert-Leucine (tert-butylglycine), tert-leucine methyl ester, GlyValOMe, and Leu- AlaOMe with the chloro-bridged complexes [Cp*IrCl2]2, [(p-cymene)RuCl2]2 or [(C6Me6)RuCl2]2 in the presence of NaOMe give the complexes [Cp*Ir(Cl)NH2CH(R)CO2] (1), [(p-cymene)Ru(Cl)- NH2CH(R)CO2] (2), Cp*Ir(Cl2)[NH2CH(R)CO2Me] (5), {(C6Me6)Ru(Cl)[NH2CH2CONHCH(R)- CO2Me]}+Cl− (6), [Cp*Ir(Cl)NH2CH2CONCH(R)CO2Me] (7), [Cp*Ir(Cl)NH2CH(CH2CHMe2)- CONCH(R)CO2Me)] (8), and Cp*Ir(Cl2)[NH2CH2CONHCH(R)CO2Me) (9). With pentaglycine the complexes [Cp*Ir(Cl2)(pentaglycinate+Na+)] (10) and [(C6Me6)Ru(pentaglycineOMe- H+)] (11) could be isolated. Coordination of one equivalent of the S-protected tripeptide glutathione to [Cp*Ir(Cl)] and to [(C6Me6)Ru(Cl)] was observed. Some in situ prepared (p-cymene)Ru complexes with deprotonated dipeptide esters were tested as catalysts and the complex [(p-cymene)Ru(Cl)(NH2CH(CHMeEt)NCH (CHMe2)CO2tert-Bu)] gave a yield of 73% and moderate entantiomeric excess (36% ee)...
Angewandte Chemie
3] a) P. M. Maitlis, M. L. Games, zyxwvutsrqponm J. zyxwvutsrqponml Am. Chem. zyxwvutsrqp Soc. zyxwvutsrq 85 (1963) 1887, denen ,,weiche" Kationen als elektrophile Zentren fixiert sindf3I. Daruber hinaus zeigten wir, daR in solchen Metallo-Makrocyclen harte Kationen wie Alkali-und Erdalkali-Kationen cokomplexiert werden konnen und so heteronucleare zweikernige Komplexe gebildet werdenI4' ' I. Wir beschreiben nun die Synthese des Barium-Komplexes eines neuartigen makrocyclischen Liganden und dessen Reaktion rnit Kup-b) P. M. Maitlis, Adv. Organornet. Chem. 4 (1966) 95. zyxwvutsrqp [4] H. Werner, Angec. Chem. 89 (1977) 1; Angew. Chem. zyxwvutsrqp Int. Ed. Engl. 16 (1977) I; [(~-~3-2-MeC,H,)(~-Cp)(~d(pph,)J,1(pd-pd):
Zeitschrift für Naturforschung B, 1983
Carbene Transfer, Metal-Metal Multiple Bonds Carbene transfer from aliphatic diazoalkanes upon coordinatively unsaturated metal centers is a general synthetic concept that provides straightforward routes into organometallic hydrocarbon chemistry. A comparison focussing on several key reactions of general applicability demonstrates that mononuclear organometal substrates add carbenes that may act as bridging ligands (e.g., compound 6) if they arise from u>,co'-bisdiazoalkanes. By way of contrast, metal-metal double bonds cleanly form dimetallacyclopropane-type derivatives under very mild conditions (7-9). The broadest variety of structures is finally encountered with metal-metal triply bonded precursors such as the molybdenum compounds 3: here, the initial diazoalkane adducts are subject to further rearrangement processes commonly leading to metal-metal single bonds (11) or causing irreversible cleavage of the dinuclear metal systems (10).
Zeitschrift für Naturforschung. B, A journal of chemical sciences, 2005
AlaOMe with the chloro-bridged complexes [Cp * IrCl 2 ] 2 , [(p-cymene)RuCl 2 ] 2 or [(C 6 Me 6)RuCl 2 ] 2 in the presence of NaOMe give the complexes [Cp * Ir(Cl)NH 2 CH(R)CO 2 ] (1), [(p-cymene)Ru(Cl)-NH 2 CH(R)CO 2 ] (2), Cp * Ir(Cl 2)[NH 2 CH(R)CO 2 Me] (5), {(C 6 Me 6)Ru(Cl)[NH 2 CH 2 CONHCH(R)-CO 2 Me]} + Cl − (6), [Cp * Ir(Cl)NH 2 CH 2 CONCH(R)CO 2 Me] (7), [Cp * Ir(Cl)NH 2 CH(CH 2 CHMe 2)-CONCH(R)CO 2 Me)] (8), and Cp * Ir(Cl 2)[NH 2 CH 2 CONHCH(R)CO 2 Me) (9). With pentaglycine the complexes [Cp * Ir(Cl 2)(pentaglycinate + Na +)] (10) and [(C 6 Me 6)Ru(penta-glycineOMe-H +)] (11) could be isolated. Coordination of one equivalent of the S-protected tripeptide glutathione to [Cp * Ir(Cl)] and to [(C 6 Me 6)Ru(Cl)] was observed. Some in situ prepared (p-cymene)Ru complexes with deprotonated dipeptide esters were tested as catalysts and the complex [(p-cymene)Ru(Cl)(NH 2 CH(CHMeEt)NCH (CHMe 2)CO 2 tert-Bu)] gave a yield of 73% and moderate entantiomeric excess (36% ee) in the transfer hydrogenation of acetophenone to 2-propanol.
Journal of organometallic …, 1993
Treatment of Ir(CH,XCOXPPh,), with molybdenum or tungsten hydrides Cp(CO),MH results in elimination of both CH, and CO to give heterobimetallic products of composition Cp(COlM&-CO),Ir(PPh,), (1: M = MO; 2: M = W). Degradation of these complexes in solution occurs by CO transfer and oxidative P-C addition, affording the phosphido-bridged derivatives Cp(CO)z-M(~-Ph,P)Ir(C,H,XCO),(PPh,) (3: M = MO; 4: M = W) as the ultimately stable compounds. The structures of 1 and 2, determined by X-ray crystallography, comprise Cp(COl,M groups attached to the Ir(PPh,)z moiety by short metal-metal bonds (Mo-Ir 2579(l), W-Ir 2583(l) A) and two asymmetric CO bridges. Zusammenfassung Die Reaktion zwischen Ir(CH,XCOXPPh,), und den Molybdln oder Wolframhydriden Cp(COl,MH ergibt unter Eliminerung von CH, und CO die heterobimetallischen Produkte Cp(CO)M&-CO),Ir(Pph,), (1: M = MO; 2: M = WI. In Liisung werden diese durch CO-fibertragung und oxidative P-C-Addition zu den phosphido-verbriickten Derivaten Cp(CO),M&PhzPNr-(C,H,)(CO)z(PPh,) (3: M = MO; 4: M = W) als letztendlich stabilen Verbindungen abgebaut. Die rontgenographisch ermittelten Strukturen von 1 und 2 enthalten Cp(CO),M-Bausteine, die fiber kurze Metall-Metall-Bindungen (Mo-Ir 2.57901, W-Ir 2.583(l) A) und zwei asymmetrische CO-Briicken an das Ir(PPh,)z-Fragment gekniipft sind.