59 research outputs found
New Câ§Nâ§C Bis-Cyclometalated Platinum(II) Complexes: Synthesis, Structures, and Photophysical Properties
Solid-state interconversions: Unique 100% reversible transformations between the ground and metastable states in single-crystals of a series of nickel( II) nitro complexes
The solid-state, low-temperature linkage isomerism in a series of five square planar groupâ
10 phosphino nitro complexes have been investigated by a combination of photocrystallographic experiments, Raman spectroscopy and computer modelling. The factors influencing the reversible solid-state interconversion between the nitro and nitrito structural isomers have also been investigated, providing insight into the dynamics of this process. The cis-[Ni(dcpe)(NO2)2] (1) and cis-[Ni(dppe)(NO2)2] (2) complexes show reversible 100â% interconversion between the Ρ1-NO2 nitro isomer and the Ρ1-ONO nitrito form when single-crystals are irradiated with 400â
nm light at 100â
K. Variable temperature photocrystallographic studies for these complexes established that the metastable nitrito isomer reverted to the ground-state nitro isomer at temperatures above 180â
K. By comparison, the related trans complex [Ni(PCy3)2(NO2)2] (3) showed 82â% conversion under the same experimental conditions at 100â
K. The level of conversion to the metastable nitrito isomers is further reduced when the nickel centre is replaced by palladium or platinum. Prolonged irradiation of the trans-[Pd(PCy3)2(NO2)2] (4) and trans-[Pt(PCy3)2(NO2)2] (5) with 400â
nm light gives reversible conversions of 44 and 27â%, respectively, consistent with the slower kinetics associated with the heavier members of groupâ
10. The mechanism of the interconversion has been investigated by theoretical calculations based on the model complex [Ni(dmpe)Cl(NO2)]
High-pressure crystallographic and spectroscopic studies on two molecular dithienylethene switches
A DFT based investigation into the electronic structure and properties of hydride rich rhodium clusters
CâC Ď complexes of rhodium
In this article, the complexes [Rh(Binor-Sâ˛)(PR(3))][BAr(4)(F)] (R = (i)Pr, Cy, C(5)H(9)) are described. A combination of x-ray crystallography, NMR spectroscopy, density functional theory, and âatoms in moleculesâ calculations unequivocally demonstrates that the complexes contain rare examples of metal¡¡¡C [Image: see text] C agostic interactions. Moreover, they are fluxional on the NMR time scale, undergoing rapid and reversible C [Image: see text] C activation. Kinetic data and calculations point to a bismetallacyclobutane, Rh(V), intermediate
Experimental charge density study into CâC Ď-interactions in a Binor-S rhodium complex
Transition-metal complexes containing (CâC)âM s-interactions have potential applications in both
catalysis and the activation and cleavage of CâC bonds. Fully characterising the bonding and
interactions in complexes containing such (CâC)âM s-interactions is vital to understand their
chemical behaviour. As a result a high-resolution experimental X-ray charge density study has been
undertaken on [Rh(Binor-S)(PCy3)][HCB11Me11] (Binor-S = 1,2,4,5,6,8-dimetheno-s-indacene) which
contains a (CâC)âRh interaction. The data are analysed using Baderâs âAtoms in Moleculesâ (AIM)
approach with particular attention paid to the interactions around the rhodium centre. The results
provide clear evidence for the s(CâC)âRh interaction in the solid-state which is classified as a weak
covalent interaction. These results are supported by theoretical calculations
CCDC 799182: Experimental Crystal Structure Determination
An entry from the Cambridge Structural Database, the worldâs repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures
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