Reactivity and fluxionality of late transition metal cluster compounds
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For the low-spin t2g6 Ru(OH2)62+ (ΔV⧧ = −0.4 cm3 mol-1) and Rh(OH2)63+ (ΔV⧧ = −4.2 cm3 mol-1) hexaaquaions, the respective Id and Ia water exchange mechanisms had been assigned, mainly on the basis of activation volumes ΔV⧧ and entering ligands effects for ...
The synthesis of [PPN][IrRu3(CO)13] and [PPN][IrOs3(CO)13] from the reaction of [PPN][Ir(CO)4] with M3(CO)12 (M = Ru or Os) is discussed. [PPN][IrRu3(CO)13] is a red-brown microcryst. powder, while [PPN][IrOs3(CO)13] is an orange-red microcryst. powder. Bo ...
The reaction of the cluster complexes [Pt-3(mu -CO)(3)(PR3)(3)] (PR3 = PPh3 1, PPh(2)Bz 2, PCy3 3 and P(i)pr(3) 4) with dialkyl acetylenedicarboxylate, R'O2CC drop CCO2R' (R= CH3 or Bu-t) have been examined under various conditions. At low temperature the ...
[Pt-3(mu-CO)(3)(PPh3)(3)] was prepared in high yield by the reaction of [Pt-3(mu-CO)(3)(PPh3)(4)] with H2O2. The carbonyl ligands in [Pt-3(mu-CO)(3)(PR3)(3)] (PR3 = PPh3, PPh(2)Bz, PCy3, P'Pr-3) may be completely replaced by sulfur dioxide to give [Pt-3(mu ...
The lithium enolate of(+/-)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-o ne (16) added to furan-2-carboxaldehyde giving a single aldol 19 (Schemes 1 and 2) that was converted with high stereoselectivity into (+/-)-(1RS, 3SR,4SR,5RS,6SR) ...
A Rh-103, P-31 and C-13 NMR study of [Rh-4(CO)(6)(mu-PPh2)(4)] in CD2Cl2 indicates that the strongly bonded, bridging, anionic ligand PPh2- takes part in the site exchange of the carbonyl ligands and is actually mobile about the metallic surface of this cl ...
The reaction of (E)-bis(2,4,6-tri-tert-butylphenyl)diphosphene with Ru-3(CO)(12) results in cleavage of the P=P bond with concomitant C-H activation of one of the t-butyl groups to form Ru-3(mu-H)(2)(CO)(8)(mu-P-C6H2-2,4-Bu-t(2)-6-CMe2CH2)(2). The H-atoms ...
A stepwise approach to the development of artificial O6-alkylguanine-DNA alkyltransferases (AGTs) and its application to the in vitro selection of antibodies with highly reactive cysteine residues are described. As a result of low reactivity of O6-alkylate ...
An efficient synthesis of cycloisodityrosine was developed based on an intramol. nucleophilic arom. substitution reaction for the selective ring formation of a key biaryl ether intermediate. Cycloetherification of dipeptide I gave exclusively the (meta,par ...
[Pt-3(mu-CO)(3)(PPh3)(3)] was prepared in high yield by the reaction of [Pt-3(mu-CO)(3)(PPh3)(4)] with H2O2. The carbonyl ligands in [Pt-3(mu-CO)(3)(PR3)(3)] (PR3 = PPh3, PPh(2)Bz, PCy3, P'Pr-3) may be completely replaced by sulfur dioxide to give [Pt-3(mu ...
