Biomedical subjects
Publications and source records attributed to Feliu Maseras.
Structural, spectroscopic and theoretical evidence indicate that an unusual alpha-C-C agostic interaction is preferred over both alpha- and beta-C-H agostic alternatives in the title compound, TpMe2NbCl(c-C3H5)(MeCCMe).
DFT methods are used to quantify the relationship between M-C and H-C bond energies; for MLn = Re(eta5-C5H5)(CO)2H and fluorinated aryl ligands, theoretical and experimental investigations of ortho-fluorine substitution indicate a much larger increase in the M-C than in the H-C bond energy, so stabilising C-H activation products.
The application of quantum mechanics/molecular mechanics (QM/MM) methods in transition metal chemistry is growing steadily. It becomes therefore appropriate to assess the importance of a number of technical issues associated to their implementation. This work presents the discussion of several of these issues, including the eventual need for conformational searches, the choice of the MM force field and the possibility of its tuning. The examples presented here prove that a proper handling of these technical aspects can lead to an improvement in the efficiency and quality of QM/MM calculations.
DFT (B3LYP) calculations have been carried out in order to quantitatively evaluate the energies and stereochemistry of the accessible structures of [(dhpe)Pt(SiHR(2))](+) (dhpe = H(2)P-CH(2)-CH(2)-PH(2); R = H, CH(3), SiH(3), Cl, OMe, SMe, NMe(2)) and of [(dhpe)Pt(SiR(3))](+) (R = CH(3), Cl). A number of different isomers have been located. The expected terminal silyl or hydrido-silylene complexes are often not the most stable complexes. An isomer in which an H or an R group bridges a Pt=SiHR or Pt=SiR(2) bond is found to compete with the terminal silyl or hydrido-silylene isomers. In some cases, isomers derived from cleavage of a C-H bond and formation of a silene or disilene ligand are obtained. The structures of the platinum silyls differ from that of the equivalent alkyl complex, calculated for [(dhpe)Pt(CH(3))](+).
Reaction of the hexahydride complex OsH(6)(P(i)Pr(3))(2) (1) with pyridine-2-thiol leads to the trihydride derivative OsH(3){kappa-N,kappa-S-(2-Spy)}(P(i)Pr(3))(2) (2). The structure of 2 has been determined by X-ray diffraction. The geometry around the osmium atom can be described as a distorted pentagonal bipyramid with the phosphine ligands occupying axial positions. The equatorial plane contains the pyridine-2-thiolato group, attached through a bite angle of 65.7(1) degrees, and the three hydride ligands. The theoretical structure determination of the model complex OsH(3){kappa-N,kappa-S-(2-Spy)}(PH(3))(2) (2a) reveals that the hydride ligands form a triangle with sides of 1.623, 1.714, and 2.873 Å, respectively. A topological analysis of the electron density of 2a indicates that there is no significant electron density connecting the hydrogen atoms of the OsH(3) unit. In solution, the hydride ligands of 2 undergo two different thermally activated site exchange processes, which involve the central hydride with each hydride ligand situated close to the donor atoms of the chelate group. The activation barriers of both processes are similar. Theoretical calculations suggest that the transition states have a cis-hydride-dihydrogen nature. In addition to the thermally activated exchange processes, complex 2 shows quantum exchange coupling between the central hydride and the one situated close to the sulfur atom of the pyridine-2-thiolato group. The reactions of 1 with L-valine and 2-hydroxypyridine afford OsH(3){kappa-N,kappa-O-OC(O)CH[CH(CH(3))(2)]NH(2)}(P(i)Pr(3))(2) (3) and OsH(3){kappa-N,kappa-O-(2-Opy)}(P(i)Pr(3))(2) (4) respectively, which according to their spectroscopic data have a similar structure to that of 2. In solution, the hydride ligands of 3 and 4 also undergo two different thermally activated site exchange processes. However, they do not show quantum exchange coupling. The tetranuclear complexes [(P(i)Pr(3))(2)H(3)Os(&mgr;-biim)M(TFB)](2) [M = Rh (5), Ir (6); H(2)biim = 2, 2'-biimidazole; TFB = tetrafluorobenzobarrelene] have been prepared by reaction of OsH(3)(Hbiim)(P(i)Pr(3))(2) with the dimers [M(&mgr;-OMe)(TFB)](2) (M = Rh, Ir). In solution the hydride ligands of these complexes, which form two chemically equivalent unsymmetrical OsH(3) units, undergo two thermally activated site exchanges and show two different quantum exchange coupling processes.
A theoretical study including full geometry optimizations is carried out at the IMOMM(MP2:MM3) (IMOMM = integrated molecular orbital molecular mechanics) computational level on the [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] systems, the results being compared with available experimental diffraction data, as well as with MP2 results on the model system [ReH(5)(PH(3))(2)(SiH(3))(2)]. A simple scheme for the analysis of the relative weight of different contributions to the "steric" distortion is also proposed and applied to the same [ReH(5)(PPh(i)()Pr(2))(2)(SiHPh(2))(2)] and [ReH(5)(PCyp(3))(2)(SiH(2)Ph)(2)] species.
The dihydrido-olefin complex OsH(2)(eta(2)-CH(2)=CHEt)(CO)(P(i)Pr(3))(2) (2) reacts with H(2)SiPh(2) to give OsH(3)(SiHPh(2))(CO)(P(i)Pr(3))(2) (3). The molecular structure of 3 has been determined by X-ray diffraction (monoclinic, space group P2(1)/c with a = 16.375(2) Å, b = 11.670(1) Å, c =18.806(2) Å, beta = 107.67(1) degrees, and Z = 4) together with ab initio calculations on the model compound OsH(3)(SiH(3))(CO)(PH(3))(2). The coordination geometry around the osmium center can be rationalized as a heavily distorted pentagonal bipyramid with one hydrido ligand and the carbonyl group in the axial positions. The two other hydrido ligands lie in the equatorial plane, one between the phosphine ligands and the other between the SiHPh(2) group and one of the phosphine ligands. Complex 3 can also be prepared by reaction of OsH(eta(2)-H(2)BH(2))(CO)(P(i)Pr(3))(2) (4) with H(2)SiPh(2). Similarly, the treatment of 4 with HSiPh(3) affords OsH(3)(SiPh(3))(CO)(P(i)Pr(3))(2) (5), while the addition of H(3)SiPh to 4 in methanol yields OsH(3){Si(OMe)(2)Ph}(CO)(P(i)Pr(3))(2) (6). Complex 2 also reacts with HGeR(3) and HSnR(3) to give OsH(3)(GeR(3))(CO)(P(i)Pr(3))(2) (GeR(3) = GeHPh(2) (7), GePh(3) (8), GeEt(3) (9)) and OsH(3)(SnR(3))(CO)(P(i)Pr(3))(2) (R = Ph (10), (n)Bu (11)), respectively. In solution, compounds 3 and 5-11 are fluxional and display similar (1)H and (31)P{(1)H} NMR spectra, suggesting that they possess a similar arrangement of ligands around the osmium atom.