Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes.

The addition of an excess of phenyldiazomethane to chlorobenzene solutions of the cationic dinitrosyl bisphosphine rhenium(-I) complexes [Re(NO)2(PR3)2][BAr(F)4] (R = Cy 1a, R = (i)Pr 1b) gave the corresponding benzylidene complexes [Re{=CH(C6H5)}(NO)2(PR3)2][BAr(F)4] (2a and 2b) in good yields. The treatment of 2b with dioxygen resulted in the oxidation of one of the nitrosyl ligands into the corresponding eta2-nitrito (3b) and nitrato complexes (4b) both in the solid state and in solution. In the case of the tricyclohexylphosphine derivative 2a the analogous conversion was not observed. A mechanism for the reaction of 2b with O2 is proposed which is based on an initial SET to the O2 molecule and subsequent formation of a peroxynitrite complex followed by the formation of a dinuclear mU-N2O4 intermediate. This in turn would undergo fission of the peroxo bond to afford 3b. A related sequence of steps is anticipated for the transformation of 3b to 4b. Furthermore, a similar mechanism seems reasonable for the seemingly topochemical reaction of 2b to 3b and 4b in the solid state. The initial SET to dioxygen and subsequent formation of the peroxynitrite complex is supported by DFT calculations on the trimethylphosphine model complexes [Re=CH{C6H5})(NO)2(PMe3)2]n+ (n = 1 and 2).

Metal nitrosyl reactivity: Acetonitrile-promoted insertion of an alkylidene into a nitrosyl ligand with fission of the NO bond.

Treatment of the complexes [Re(NO)2(PR3)2][BAr(F)4] (R = Cy, 1 a; R = iPr, 1 b) with phenyldiazomethane gave the cationic benzylidene species [Re{CH(C6H5)}(NO)2(PR3)2][BAr(F)4] (2 a and 2 b) in good yields. Upon reaction of 2 a and 2 b with acetonitrile, the consecutive formation of [Re(N[triple bond]CCH3)(N[triple bond]CPh)(NO)(OC(CH3)=NH)(PR3)][BAr(F)4] (3 a and 3 b) and [Re(NCCH3)(OC{CH3}NH{C6H5})(NO)(PR3)2][BAr(F)4] (4 a and 4 b) was observed. The proposed reaction sequence involves the coupling of coordinated NO, carbene and acetonitrile molecules to yield the (1Z)-N-[imino(phenyl)methyl]ethanimidate ligand. The coupling of the nitrosyl and the benzylidene is anticipated to occur first, forming an oximate species. The subsequent acetonitrile addition can be envisaged as a heteroene reaction of the oximate and the acetonitrile ligand yielding 3 a and 3 b, which in turn can cyclise and undergo a prototropic shift initiated by an internal attack of the ethaneimidate ligand on the benzonitrile moiety to afford 4 a and 4 b.

Dicarbonyl-nitrosyl-complexes of rhenium (Re) and technetium (Tc), a potentially new class of compounds for the direct radiolabeling of biomolecules.

Re- and Tc-complexes of the oxidation state (+I) offer a useful synthetic pool for the labeling of biomolecules due to their co-ordination properties and stability, which are superior to compounds of the oxidation state (+V). Based on the results for Tc-tricarbonyl complexes it was the topic of this work to develop an access to similar but higher charged compounds, which could be performed by replacing a neutral [CO]-group by a [NO](+)-group. The resulting Re(I)- and Tc(I)-dicarbonyl-nitrosyl complexes, such as [N(CH2CH3)4][ReX3(CO)2(NO)], show a tendency for co-ordination at carboxylic and amine groups of biomolecules (X = Br, Cl). This was shown with picolinic acid (H-pic), a suitable model for amino acids, forming the neutral complex [ReX(pic)(CO)2(NO)]. In a similar fashion conjugation of [188Re(CO)2(NO)](2+)- or [99mTc(CO)2(NO)](2+)-compounds to proteins or antibodies is feasible. This approach opens a way to a potentially new class of radiopharmaceuticals.

Electronic Communication in C(4)-Bridged Binuclear Complexes with Paramagnetic Bisphosphane Manganese End Groups.

Building blocks for conducting polymers or NLO materials are the linear, unsaturated carbon chain bridged manganese complexes 1(n+) (n=0-2). All oxidation states were investigated spectroscopically and by X-ray structure determinations. The analytical data confirm a communication of the electrons over the C(4) chain-a prerequisite for electrical conductivity and NLO properties of oligo- or polymeric materials.

An improved aerosol generator.

An aerosolizer has been developed which automatically compensates for changes in the concentration and volume of a solution during aerosolization by adjustment of the temperature and pressure of the atomizing air jet. It represents the redesign of a generator previously used for short-term inhalation exposures (one-half to a few hours) where variability in solution concentration was not of great concern and solutions could be replenished daily. The stability of the original generator was quite inadequate, and it was not satisfactory for production of aerosols of constant physical characteristics over longer or repetitive time periods or where a minimum of manipulation is required--viz., for radioactive and other highly noxious materials. The redesigned aerosolizer should be valuable for long-term or repetitive use, since it requires no cleaning, merely refilling, and can 0e made as small or as large as experimental needs require. It should be particularly useful where correlations between the amount of deposition and aerosol characteristics are being studied.