Organophosphorus Ligands in Studies of Metal Complexes. Investigations of Ligand Exchange and Multielement Trace Analysis using Dithiophosphinic Ligands

Abstract

On mixing organic solutions of [Et₂PS₂]M/n and [Prop₂PS₂]M/n [M=Pd(II), Pt(II), Rh(III), lr(III), Cr(III)] an equilibrium is obtained containing statistical amounts of the corresponding mixed ligand complexes as can be shown by 31P{¹H}-NMR, HPLC and FD-MS. With Pt(II)- and Pd(II)-chelates the kinetics of ligand exchange was determined by HPLC. Mixed complexes ML₂L′ and MLL′₂ were isolated from the equilibrium solutions in case of the more inert Cr(III)-, Rh(III)- and lr(III)-chelates by preparative HPLC. Pd(II), Pt(II) and Rh(III) can be determined quickly and simultaneously in aqueous solutions at nanogramm level by complexation with Et₂PS₂? in a modified sample loop followed by reversed phase HPLC.     

Silazanes plus MCl4-substitution vs. rearrangement reactions

Novel silicon and tin compounds were synthesized by the reaction of lithium salts of 1,3-di-phenyl-1,1,3,3-tetramethyldisilazane H(DPTMDS) and 1,1,3,3,5,5-hexamethylcyclotrisilazane H₃(HMCTS) with SiCl₄ and SnCl₄, respectively. The reactions with H(DPTMDS) yield the substitution products (DPTMDS)₂SiCl₂ and (DPTMDS)₂SnCl₂. In contrast, the reactions with the cyclic silazane H₃(HMCTS) lead to a large variety of products due to the competition of substitution reactions and ring contractions. The resulting new compounds were characterized by elemental analyses, NMR spectroscopy, and single crystal X-ray structure analyses. Dedicated to Prof. Edmunds Lukevics on the occasion of his 70th birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1845–1856, December, 2006.     

Intrinsic noise properties of atomic point contact displacement detectors

We measure the noise added by an atomic point contact operated as a displacement detector. With a microwave technique, we increase the measurement speed of atomic point contacts by a factor of 500. The measurement is then fast enough to detect the resonant motion of a nanomechanical beam at frequencies up to 60 MHz and sensitive enough to observe the random thermal motion of the beam at 250 mK. We demonstrate a shot-noise limited imprecision of 2.3 fm/square root[Hz] and observe a 78 aN/square root[Hz] backaction force, yielding a total uncertainty in the beam's displacement that is 42 times the standard-quantum limit.     

Electronic structure of high-spin iron(III)-alkylperoxo complexes and its relation to low-spin analogues: reaction coordinate of O-O bond homolysis.

The spectroscopic properties of the high-spin Fe(III)-alkylperoxo model complex [Fe(6-Me(3)TPA)(OH(x))(OO(t)Bu)](x)(+) (1; TPA = tris(2-pyridylmethyl)amine, (t)Bu = tert-butyl, x = 1 or 2) are defined and related to density functional calculations of corresponding models in order to determine the electronic structure and reactivity of this system. The Raman spectra of 1 show four peaks at 876, 842, 637, and 469 cm(-1) that are assigned with the help of normal coordinate analysis, and corresponding force constants have been determined to be 3.55 mdyn/A for the O-O and 2.87 mdyn/A for the Fe-O bond. Complex 1 has a broad absorption feature around 560 nm that is assigned to a charge-transfer (CT) transition from the alkylperoxo to a t(2g) d orbital of Fe(III) with the help of resonance Raman profiles and MCD spectroscopy. An additional contribution to the Fe-O bond arises from a sigma interaction between and an e(g) d orbital of iron. The electronic structure of 1 is compared to the related low-spin model complex [Fe(TPA)(OH(x))(OO(t)Bu)](x)(+) and the reaction coordinate for O-O homolysis is explored for both the low-spin and the high-spin Fe(III)-alkylperoxo systems. Importantly, there is a barrier for homolytic cleavage of the O-O bond on the high-spin potential energy surface that is not present for the low-spin complex, which is therefore nicely set up for O-O homolysis. This is reflected by the electronic structure of the low-spin complex having a strong Fe-O and a weak O-O bond due to a strong Fe-O sigma interaction. In addition, the reaction coordinate of the Fe-O homolysis has been investigated, which is a possible decay pathway for the high-spin system, but which is thermodynamically unfavorable for the low-spin complex.