42 research outputs found
Bis(6-diphenylphosphino-acenaphth-5-yl)sulfoxide. A New Ligand for Late Transition Metal Complexes
The synthesis of the new ligand bis(6-diphenylphosphinoacenaphth-5-yl)sulfoxide, [6-(Ph2P)-5-Ace-6](2)-SO (1), is presented along with six transition metal complexes thereof, namely,1 center dot MCl (M = Rh, Cu, Ag, Au) and1 center dot MCl2(M = Ni, Pd). Within these novel complexes, close metal-sulfur distances are observed and the nature of the M-S coordination, as well as the response of the(+)S-O(-)bond, are investigated in detail with a set of spectroscopic, crystallographic and real-space bonding indicators
The effects of experimentally obtained electron correlation and polarization on electron densities and exchange-correlation potentials
Peri-substituted phosphorus-tellurium systems â an experimental and theoretical investigation of the PâââTe through-space interaction
The authors are thankful to the EPSRC, the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea, the School of Chemistry St. Andrews, and EaStCHEM for support.A series of peri-substituted phosphorus-tellurium systems RâTeâAcenapâPR2 (Râ = Ph, p-An, Nap, Mes, Tip; R = iPr, Ph) exhibiting large âthrough spaceâ spin-spin coupling constants and the âonsetâ of three-centre four-electron type interactions are presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metal-coordination (Pt, Au) is discussed using NMR spectroscopy, single crystal X-ray diffraction, and advanced DFT studies including NBO, AIM and ELI-D analyses.PostprintPeer reviewe
Lattice response to the radiation damage of molecular crystals: radiation-induced versus thermal expansivity.
The interaction of intense synchrotron radiation with molecular crystals frequently modifies the crystal structure by breaking bonds, producing fragments and, hence, inducing disorder. Here, a second-rank tensor of radiation-induced lattice strain is proposed to characterize the structural susceptibility to radiation. Quantitative estimates are derived using a linear response approximation from experimental data collected on three materials Hg(NO3)2(PPh3)2, Hg(CN)2(PPh3)2 and BiPh3 [PPh3 = triphenylphosphine, P(C6H5)3; Ph = phenyl, C6H5], and are compared with the corresponding thermal expansivities. The associated eigenvalues and eigenvectors show that the two tensors are not the same and therefore probe truly different structural responses. The tensor of radiative expansion serves as a measure of the susceptibility of crystal structures to radiation damage
Bis(6-Diphenylphosphinoacenaphth-5-yl)Telluride as a Ligand toward Manganese and Rhenium Carbonyls
The reaction of the previously known bis(6-diphenylphosphinoacenaphthyl-5-)telluride (6-Ph2P-Ace-5-)2Te (IV) with (CO)5ReCl and (CO)5MnBr proceeded with the liberation of CO and provided fac-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (fac-1: M = Re, X = Cl; fac-2: M = Mn, X = Br), in which IV acts as bidentate ligand. In solution, fac-1 and fac-2 are engaged in a reversible equilibrium with mer-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (mer-1: M = Re, X = Cl; mer-2: M = Mn, X = Br). Unlike fac-1, fac-2 is prone to release another equivalent of CO to give (6-Ph2P-Ace-5-)2TeMn(Br)(CO)2 (3), in which IV serves as tridentate ligand
Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives
The syntheses and full characterizations of the periâsubstituted naphthalenes (Nap) and acenaphthenes (Ace) 1âBrâ8â(Ph2P)âNap (1a) and 5âBrâ6â(Ph2P)âAce (1b), as well as their derivatives 1âBrâ8â[Ph2P(E)]âNap [E = CH3+ (counterion Iâ) (2a); E = O (3a); E = S (4a); E = Se (5a)] and 5âBrâ6â[Ph2P(E)]âAce [E = CH3+ (counterion Iâ) (2b); E = O (3b); E = S (4b); E = Se (5b)] are reported. In order to quantify the energetic and electronic effects of the periâinteractions, an additional set of molecules, 1câ5c, with the bromine atom and the Ph2P(E) fragment on opposite sides of the naphthalene group was generated, which serves as reference because 1câ5c exhibit negligible periâinteractions. The molecular arrangements of all 15 compounds were optimized at the B3PW91/6â311+G(2df, p) level of theory. The analysis of the periâinteractions was not only based on the inspection of the molecular arrangement and energies alone, but extended to a set of realâspace bonding indicators (RSBI). These indicators were derived from theoretically calculated electron densities and pair densities, respectively. Particularly, the stockholder, AtomsâInâMolecules (AIM) and ElectronâLocalizabilityâIndicator (ELIâD) space partitioning schemes were used to produce Hirshfeld surfaces (HS), bond topological properties and basins of localized bonding and nonbonding electron pairs. Since 1câ5c are 35â58 kJ·molâ1 lower in energy than their counterparts 1aâ5a, the hypothesis of a mainly repulsive periâinteraction in 1a/bâ5a/b was confirmed. The shapes and contact patterns of the HSs of atoms and fragments involved in the periâinteractions (Br, P, E = CH3+, O, S, Se) reveal that only in 1a and 1b are periâinteractions exhibited between the bromine and the phosphorus atoms. In all other cases (2a/bâ5a/b), the interaction mainly occurs between the bromine atom and the E atom/fragment. According to the bond topological properties and the electron populations within the (non)bonding ELIâD basins, which both are almost unaffected by the BrâP/E periâinteraction, sterical interactions are characterized essentially by geometrical and energetical changes