Syntheses, characterizations, and single-crystal X-ray structures of soluble titanium alkoxide phosphonates

Reactions of Ti(OiPr)4 with different phosphonic acids RPO3H2 (R = Ph, 4-CNPh, Me, tBu) in organic solvents have been investigated. In the presence of small amounts of water, the new molecular titanium oxide alkoxide phosphonates [Ti4(mu 3-O)(OiPr)5(mu-OiPr)3(RPO3)3].DMSO [R = Ph (1), Me (2), tBu (3), 4-CNPh (4)] were isolated. The single-crystal X-ray structure analyses of 1 and 2 revealed hexacoordinated titanium atoms and a connectivity of (111) for each phosphonate. Under rigorous exclusion of water, the reaction of Ti(OiPr)4 with tert-butylphosphonic acid in toluene gave the titanium phosphonate tetramer [Ti(OiPr)2(tBuPO3)]4 (5). A single-crystal X-ray structure analysis of 5 revealed a 5 + 1 coordination of the titanium atoms as a result of the (112) connectivity of each phosphonate; such a coordination mode has never been reported for a titanium phosphate, phosphonate, or phosphinate. Compounds 1-5 were characterized by FT-IR, 31P MAS NMR, and solution multinuclear NMR (1H, 13C(1H,) 31P(1H)) spectroscopies. 13C CP MAS NMR experiments were carried out on arylphosphonates 1 and 4. Solution NMR experiments were also used to investigate the exchange reaction between 1 and 2 and the conversion of 5 to [Ti4(mu 3-O)(OiPr)5(mu-OiPr)3(tBuPO3)3].iPrOH by partial hydrolysis in the presence of Ti(OiPr)4. The phosphonate clusters 1-5 are soluble in organic solvents and are likely intermediates in the sol-gel processing of inorganic-organic hybrids based on titanium oxide and phosphonate groups that we are currently developing.     

Isolation and Spectroscopic Characterization of New Endohedral Fullerenes in the Size Gap of C74 to C76

New alkaline earth metal endohedral fullerenes Sr@C₇₄, Sr@C₇₆‐I, II and Ca@C₇₄, prepared by means of the RF‐method, have been isolated using multistep HPLC. The purity was ascertained by anionic LDI TOF mass spectroscopy, considering the isotopic patterns of the compounds. The influence of the incorporated metal on the electronic structure has been studied by VIS‐NIR and Raman spectroscopy. Photoexcited triplet‐state EPR spectroscopy was used to investigate the structure of these otherwise EPR‐silent fullerenes. Displaying the frequency of the cage vs. encapsulated metal vibrational modes as a function of the square root of the reciprocal masses of the metals clearly separates the M³⁺@C_n^3— and the M²⁺@C_n^2— families. This seems to be a generally applicable tool for monitoring the metal to fullerene charge transfer.     

Structure and electric properties of Sn(N) clusters (N = 6-20) from combined electric deflection experiments and quantum theoretical studies

Electric deflection experiments have been performed on neutral Sn(N) clusters (N = 6-20) at different nozzle temperatures in combination with a systematic search for the global minimum structures and the calculation of the dielectric properties based on density functional theory. For smaller tin clusters (N = 6-11), a good agreement between theory and experiment is found. Taking theoretically predicted moments of inertia and the body fixed dipole moment into account permits a quantitative simulation of the deflected molecular beam profiles. For larger Sn(N) clusters (N = 12-20), distinct differences between theory and experiment are observed; i.e., the predicted dipole moments from the quantum chemical calculations are significantly larger than the experimental values. The investigation of the electric susceptibilities at different nozzle temperatures indicates that this is due to the dynamical nature of the tin clusters, which increases with cluster size. As a result, even at the smallest nozzle temperature of 40 K, the dipole moments of Sn(12-20) are partially quenched. This clearly demonstrates the limits of current electric deflection experiments for structural determination and demonstrates the need for stronger cooling of the clusters in future experiments.     

NMR experiment factors numbers with Gauss sums

We factor the number 157573 using an NMR implementation of Gauss sums. Although the current implementation is classical and scales exponentially, we believe that an extension to the quantum regime using entangled states is possible.     

Entangled electron and nuclear spin states in 15N@C60: density matrix tomography

Procedures of the preparation and detection of entangled electron-nuclear spin states in (15)N@C(60) by combining electron spin resonance and electron nuclear double resonance pulse techniques are presented. A quantitative evaluation of the complete density matrix is obtained by a special density matrix tomography. All four Bell states of a two qubit subsystem were analyzed and experimental decoherence times are presented. In addition, we estimate a quantum critical temperature of T(q)=7.76 K for this system at an electron spin resonance frequency of 95 GHz.     

Two New Compounds in the Group of Zinc Phenoxides and Zinc Phenylamides

The synthesis and characterization of ethyl{2‐[(phenylamino)methyl]phenoxy}zinc ( 1 ) and ethyl{2‐[(propan‐2‐ylideneamino)methyl]phenylamido}zinc ( 2 ) are reported. The phenoxide 1 was prepared starting from 2‐(phenylaminomethyl)phenol and diethylzinc and the phenylamide 2 was obtained from 2,2‐dimethyl‐1,2,3,4‐tetrahydroquinazoline and diethylzinc. The compounds were characterized by NMR spectroscopy (¹H, ¹³C{¹H}), IR spectroscopy, elemental analysis, TGA measurements, and X‐ray structure analysis. In the solid state both compounds form dimers where ( 1 )₂ · 4thf shows a planar Zn₂O₂ and ( 2 )₂ a planar Zn₂N₂ unit. Noteworthy, the aminal ring of 2,2‐dimethyl‐1,2,3,4‐tetrahydroquinazoline was opened by its reaction with diethylzinc to give an ylidene moiety at the benzylic nitrogen atom.     

High-field ESR in the metallic fullerides RbC60 and CsC60

We discuss field-dependent electron spin resonance (ESR) experiments on the orthorhombic phase of RbC₆₀ and CsC₆₀. X-and W-band measurements have been performed to determine electronic scattering rates in the metallic temperature regime from 50 to 350 K. The insulating low-temperature phase (T < 50 K) has been investigated by X-, Q-, and W-band ESR, i.e., at 9, 34 and 95 GHz, in order to clarify whether collective resonance modes of a possibly magnetic ground state can be observed.     

Reaction of the Pincer‐type Ligand {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}— with [Ph3C]+[PF6]—. Unprecedented Rearrangement and Carbon‐Carbon Bond Formation

The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu‐C₆H₂}Li ( 1 ‐Li) with [Ph₃C]⁺[PF₆]^— gave the substituted biphenyl derivative 4‐[(C₆H₅)₂CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)₂]₂‐1, 1′‐biphenyl ( 5 ) which was characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu]C₆H₂}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)₂]₂C₆H₃ ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.