Anorganische Komplexverbindungen in der analytischen Chemie IV. Nachweis und Bestimmung des Quecksilbers

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The bridging function of an apparently nonbridging ligand: dinuclear rhodium complexes with Rh(mu-SbR3)Rh as a molecular unit

Novel dinuclear rhodium complexes of the general composition [Rh2Cl2(mu-CRR')2(mu-SbiPr3)] (4-6) were prepared by thermolysis of the mononuclear precursors trans-[RhCl(=CRR')(SbiPr3)2] in excellent yield. The X-ray crystal structure analysis of 4 (R = R' = Ph) confirms the symmetrical bridging position of the stibane ligand. Related compounds [Rh2Cl2(mu-CPh2)(mu-CRR')(mu-SbiPr3)] (7, 8) with two different carbene units were obtained either from trans-[RhCl(=CPh2)(SbiPr3)2] (1) and RR'CN2 or by a conproportionation of 4 and 5 (R = R' = p-Tol) or 4 and 6 (R= Ph, R' = p-Tol), respectively. While CO reacts with 4 to give the polymeric product [[RhCl(CPh2)(CO)]n] (9), tert-butyl isocyanide replaces the bridging stibane and yields [Rh2Cl2(mu-CPh2)2(mu-CNtBu)] (10). The reaction of 4 with tertiary phosphanes PR3 leads to complete bridge cleavage and affords the mononuclear compounds trans-[RhCl(=CPh2)(PR3)2] (11-15). In contrast, treatment of 4 with SbMe3 and SbEt3 yields the related triply bridged complexes [Rh2Cl2(mu-CPh2)2(mu-SbR3)] (16, 17) by substitution of SbiPr3 for the smaller stibanes. The displacement of the chloro ligands in 4-6 and 10 by n5-cyclopentadienyl gives the dinuclear complexes [(n5-C5H5)2Rh2(mu-CRR')2] (18-20) and [(n5-C5H5)2Rh2(mu-CPh2)2(mu-CNtBu)] (21), of which 18 (R = R' = Ph) was characterized crystallographically.     

Rare-gas-induced broadening and shift of two-photon transitions to intermediate Rydberg states of atomic thallium*

Results of broadening and shift measurements of Doppler-free two-photon lines for transitions from the ground state to the Rydberg states with intermediate principle quantum numbers of atomic thallium perturbed by rare gases are reported. The rates show a distinct behaviour in this range of principle quantum numbers and significant dependence on the total angular momentum of the upper nP state. The experimental results are compared with calculations using a Van der Waals potential and a superposition of polarization and Fermi potentials. Additionally, broadening and shift rates of the transition Tl 6P _3/2 -9P _3/2 have been measured for quadrupolar as well as for mainly scalar excitation. The rates for both kinds of excitation coincide within the limits of error reflecting the small perturbation of the 6P _3/2 state compared to that of the upper 9P _3/2 state. Received: 6 August 1997 / Revised in final form: 29 November 1997 / Accepted: 11 December 1997     

Picosecond time resolved luminescence change upon saturation

A new sensitive method is reported for the measurement of picosecond duration luminescence change upon saturation from photoexcited samples. Examples of 600 ps and 20 ps lifetimes are given.     

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Time-resolved luminescence spectra in highly photo-excited CdSe at 1.8K

We report the first observation of very precise time-resolved luminescence from highly photoexcited platelets of CdSe at 1.8 K. The time dependence of both spontaneous and stimulated emission are presented. The results are taken as a further indication for the existence of an electron-hole liquid in CdSe at these excitation densities.     

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