Johannes Messelhäuser

Insertionsreaktionen von ethen und kohlenmonoxid in die SS-bindung des nido-clusters [(CO)3FeS]2 und synthese und struktur des 1,2-ethansulfenatothiolato-komplexes [(CO)3Fe]2SC2H4S(O)

Abstract Ethene is readily inserted into the SS bond of [(CO)3FeS]2(1) by photochemical activation and leads to the 1,2-ethanedithiolato complex [(CO)3FeSCH2]2 (2) in high yields. The dithiocarbonato complex [(CO)3Fe]2S2CO (3) arises in the same manner when CO is used as insertion agent. While cluster 1 could not be oxidised into the disulfur dioxide complex [(CO)3Fe]2S2O2 (5), cluster 2 was partially oxidised by m-chloroperbenzoic acid into the novel complex [(CO)3 Fe] 2 SC 2 H 4 S (O) (4), where the unsymmetrical 1,2-ethanesulfenatothiolato group acts as a bidentate bridging ligand. From X-ray structure analysis, the five atoms of the central bridging S2C2O skeleton in 4 lie exactly in the symmetry plane of the molecule.

Schwefelmonoxid als brückenligand in zwei- und dreikern-komplexen von mangan und eisen

Summary Sulfur monoxide can be incorporated into polynuclear complexes as a bridging ligand by three different methods. The manganese complex [(C 6 H 5 ) 3 P(CO) 4 Mn] 2 SO ( 1 ) is found by nucleophilic substitution at the sulfur atom of SOCl 2 by the hydrido complex (C 6 H 5 ) 3 P(CO) 4 MnH. 1 can be oxidized to the corresponding SO 2 complex 2 , which can also be obtained from (C 6 H 5 ) 3 P(CO) 4 MnH by reaction with SO 2 Cl 2 . SO-transfer reaction occurs by fragmentation of thiirane- S -oxide, C 2 H 4 SO, in the presence of η 5 -C 5 H 5 (CO) 2 MnL (L = CO, thf) yielding the dimeric manganese compound [η 5 -C 5 H 5 (CO) 2 Mn] 2 SO ( 3 ). According to X-ray structure analysis, the SO ligand in 3 acts as a 4-electron donor oriented in a symmetrical bridge position; the four atoms of the central SOMn 2 skeleton lie exactly in a plane. 3 is also obtained by directed oxidation of the bridging sulfur of [η 5 -C 5 H 5 (CO) 2 Mn] 2 S ( 4 ) by atmospheric oxygen; reaction of η 5 -C 5 H 5 Mn(CO) 2 thf with thiirane as a novel source of sulfur yields 4 . However, only one sulfur bridge in Fe 3 (CO) 9 S 2 ( 5 ) is oxidized by m -ClPBA to give the SO cluster Fe 3 (CO) 9 S(SO) ( 6 ). The different bridge positions of the SO ligand are occupied by the various bonding systems 3c–2e (in 1 ), 3c–4e (in 3 ) and 4c–4e (in 6 ); thus the SO complexes 1, 3 and 6 are the isolobal organometallic derivatives of sulfoxides ( 1 ) sulfur trioxide ( 3 ) and sulfones ( 6 ).

Laser induced CVD of gold using new precursors

Abstract The volatile compounds Me3AuPR3 (R = Me, Et) and MeAuPMe3 (Me: methyl, Et: ethyl) are used for depositing highly pure gold lines on glass substrates. The resistivity of the lines is in general close to that of bulk gold and rather independent of the evaporator temperature. The stripe geometries vary with laser power, writing speed and evaporator temperature. Stripe heights vary between 0.1 and 1 μm and stripe widths are between 40 and 160 μm. With Me3AuPMe3 deposition is possible near room temperature.

Synthese und Struktur des Ethendithiolato-Komplexes [(CO)3FeSCH2]2, einem Dihydrobenzvalen-Analogon/ Synthesis and Structure of the Ethenedithiolato Complex [(CO)3FeSCH2]2, an Analogon of Dihydrobenzvalene

Abstract The ethenedithiolato complex [(CO)3FeSCH2]2 (1) is obtained by thermal fragmentation of thiirane-S-oxide in the presence of Fe3(CO)12 in THF and by photolytic reaction of [(CO)3FeS]2 (3) with ethene, respectively. According to an X-ray structure analysis, complex 1 has the same symmetric polyhedron structure as dihydrobenzvalene 2 .

Direct writing of gold lines by laser-induced chemical vapor deposition

Stripes of gold metal were deposited by focussing an Ar+ laser (514nm) onto glass substrates in a heated vacuum cell containing the evaporator and the precursor. MeAuPMe3, Me3AuPR3 (R = Me,Et) were used as precursors. Using MeAuPMe3 or Me3AuPEt3, deposits of high quality were obtained above 40° C and 60° C evaporator temperature, respectively. With Me3AuPMe3 the same deposits of gold stripes were possible near room temperature. The stripes were characterized by scanning profilometry, electrical resistivity, SEM and SAM measurements. In general, the stripe resistivity was between 1.5 and 7 times of the bulk metal.

Laser-induced chemical vapor deposition of rhodium

Abstract We report here the laser CVD of rhodium stripes on glass substrates from volatile rhodium precursors Rh(CO) 2 dike, where dike = acac, thd, and hfa. Stripe dimensions, resistivities, and chemical composition were studied as functions of CW argon ion laser power, writing speed, and precursor vapor pressure. Stripe widths ranged from around fifteen up to hundreds of microns, and heights over 5 μm were observed. Stripe resistivities were optimal at intermediate laser powers, and ranged from 2 to 60 times that of the bulk material. The higher volatility of the hfa precursor allowed deposition to take place at room temperature.

Notizen: Gezielte Synthese des Thionylkomplexes Fe3(CO)9S(SO) durch Oxidation einer Sulfidobrücke in Fe3(CO)9S2 / Directed Synthesis of the Thionyl Complex Fe3(CO)9S(SO) by Oxidation of One Sulfido Bridge in Fe3(CO)9S2

One of the sulfido bridges in the cluster Fe3(CO)9S2 1 is oxidized by meta-chloroperbenzoic acid to give the known thionyl complex Fe3(CO)9S(SO) 2.

Laser-Induced CVD of Rhodium

Stripes of rhodium metal were deposited by focusing an Ar+ laser (514.5 nm) onto glass and polyimide substrates in a heated vacuum cell that contained Rh(CO)2acac vapor. Stripes were characterized by scanning profilometry, electrical resistivity, SEM and Auger measurements. Most stripes were 100–200 μm wide and 1–3 μm high. Very broad stripes (>500 μm) were deposited when the Rh(CO)2acac vapor pressure was greater than 1 Torr and when the laser power was more than 200 mW. Stripe resistivities were in general around 30 times that of the bulk material. Auger spectra show the presence of carbon in the stripes.