Synthesis, structure and reactivity of a terminal magnesium fluoride compound, [TpBut,Me]MgF: hydrogen bonding, halogen bonding and C-F bond formation.
ABSTRACT: The bulky tris(3-tert-butyl-5-pyrazolyl)hydroborato ligand, [TpBut,Me], has been employed to obtain the first structurally characterized example of a molecular magnesium compound that features a terminal fluoride ligand, namely [TpBut,Me]MgF, via the reaction of [TpBut,Me]MgMe with Me3SnF. The chloride, bromide and iodide complexes, [TpBut,Me]MgX (X = Cl, Br, I), can also be obtained by an analogous method using Me3SnX. The molecular structures of the complete series of halide derivatives, [TpBut,Me]MgX (X = F, Cl, Br, I) have been determined by X-ray diffraction. In each case, the Mg-X bond lengths are shorter than the sum of the covalent radii, thereby indicating that there is a significant ionic component to the bonding, in agreement with density functional theory calculations. The fluoride ligand of [TpBut,Me]MgF undergoes halide exchange with Me3SiX (X = Cl, Br, I) to afford [TpBut,Me]MgX and Me3SiF. The other halide derivatives [TpBut,Me]MgX undergo similar exchange reactions, but the thermodynamic driving forces are much smaller than those involving fluoride transfer, a manifestation of the often discussed silaphilicity of fluorine. In accord with the highly polarized Mg-F bond, the fluoride ligand of [TpBut,Me]MgF is capable of serving as a hydrogen bond and halogen bond acceptor, such that it forms adducts with indole and C6F5I. [TpBut,Me]MgF also reacts with Ph3CCl to afford Ph3CF, thereby demonstrating that [TpBut,Me]MgF may be used to form C-F bonds.
Project description:Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both C(aryl)-X and C(aryl)-CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for C(aryl)-CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively C(aryl)-I bond formation when X = I, and exclusively C(aryl)-CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)-X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)-X bond strength ultimately dictates selectivities for C(aryl)-X and C(aryl)-CF3 reductive elimination.
Project description:The syntheses of three series of complexes designed with self-complementary motifs for formation of halogen bonds between an iodotetrafluorophenyl ligand and a halide ligand at square-planar nickel are reported, allowing structural comparisons of halogen bonding between all four halides C6F4I···X-Ni (X = F, Cl, Br, I). In the series trans-[NiX(2,3,5,6-C6F4I)(PEt3)2] 1pX and trans-[NiX(2,3,4,5-C6F4I)(PEt3)2] (X = F, Cl, Br, I) 1oX, the iodine substituent on the benzene ring was positioned para and ortho to the metal, respectively. The phosphine substituents were varied in the series, trans-[NiX(2,3,5,6-C6F4I)(PEt2Ph)2] (X = F, I) 2pX. Crystal structures were obtained for the complete series 1pX, and for 1oF, 1oCl, 1oI and 2pI. All these complexes exhibited halogen bonds in the solid state, of which 1pF exhibited unique characteristics with a linear chain, the shortest halogen bond d(C6F4I···F-Ni) = 2.655(5) Å and the greatest reduction in halogen bond distance (I···F) compared to the sum of the Bondi van der Waals radii, 23%. The remaining complexes form zig-zag chains of halogen bonds with distances also reduced with respect to the sum of the van der Waals radii. The magnitude of the reductions follow the pattern F > Cl ? Br > I, 1pX > 1oX, consistent with the halogen bond strength following the same order. The variation in the I···X-Ni angles is consistent with the anisotropic charge distribution of the halide ligand. The temperature dependence of the X-ray structure of 1pF revealed a reduction in halogen bond distance of 0.055(7) Å on cooling from 240 to 111 K. Comparison of three polymorphs of 1oI shows that the halogen bond geometry may be altered significantly by the crystalline environment. The effect of the halogen bond on the 19F NMR chemical shift in the solid state is demonstrated by comparison of the magic-angle spinning NMR spectra of 1pF and 1oF with that of a complex incapable of halogen bond formation, trans-[NiF(C6F5)(PEt3)2] 3F. Halogen bonding causes deshielding of ?iso in the component of the tensor perpendicular to the nickel coordination plane. The results demonstrate the potential of fluoride ligands for formation of halogen bonds in supramolecular structures.
Project description:A p-xylyl-based macrocycle L has been synthesized and its binding properties with halides have been investigated by (1)H NMR titrations, single crystal X-ray diffraction analysis, and density functional theory (DFT) calculations. As investigated by (1)H NMR titrations, the ligand preferentially binds a halide in a 1:2 binding mode, with the association constants (in log K2) of 2.82, 2.70, 2.28, and 2.20 for fluoride, chloride, bromide, and iodide, respectively. The overall binding trend was found to be in the order of fluoride > chloride > bromide > iodide, reflecting that the binding strength correlates with the relative basicity and size of the respective halide. Crystallographic studies indicate that the ligand forms 1:2 complexes with chloride, bromide and iodide. In the chloride complex, the ligand is hexaprotonated and each chloride is held via three NH···Cl(-) bonds. The ligand is tetraprotonated for the other complexes, where each halide is H-bonded to two secondary ammonium NH(+) groups via NH···X(-) bonds. The results of DFT calculations performed on [H6L](6+) at M062x/6-311G (d,p) level in both gas and solvent phases, suggest that the ligand binds halides with the binding energy in the order of F(-) > Cl(-) > Br(-) > I(-), supporting the experimental data obtained from (1)H NMR studies. Results from DFT calculations further indicate that a 1:2 binding is energetically more favorable than a 1:1 binding of the ligand.
Project description:The title complex, [SbBr(0.33)Cl(0.67)(C(9)H(13)N)(C(9)H(12)N)]Br(0.75)Cl(0.25), exhibits substitutional disorder of both halogen atoms in the asymmetric unit, however, with different occupancies. Thus, the halogen atom bonded to Sb has 0.67?(4) occupancy for Cl and 0.33?(4) for Br, while the anionic halogen atom shows 0.75?(4) occupancy for Br and 0.25?(4) for Cl. An N-H?Cl/Br hydrogen bond is established between the cation and the halide anion. The coordination geometry of the Sb center in the cation is distorted pseudo-trigonal-bipyramidal as a result of the strong intra-molecular N?Sb coordination trans to the Sb-Cl/Br bond. The pendant arm on the second ligand is twisted away from the metal center. The compound crystallizes as a racemate, i.e. a mixture of (R(N2),C(Sb1)) and (S(N2),A(Sb1)) isomers with respect to planar chirality induced by the coordinating N atom and chelate-induced Sb chirality. These isomers are associated through C(phen-yl)-H?Cl/Br hydrogen bonds, forming a three-dimensional architecture.
Project description:6,6''-Bis(2,4,6-trimethylanilido)terpyridine (H2Tpy(NMes)) was prepared as a rigid, tridentate pincer ligand containing pendent anilines as hydrogen bond donor groups in the secondary coordination sphere. The coordination geometry of (H2 Tpy(NMes))copper(I)-halide (Cl, Br and I) complexes is dictated by the strength of the NH-halide hydrogen bond. The Cu(I)Cl and Cu(II)Cl complexes are nearly isostructural, the former presenting a highly unusual square-planar geometry about Cu(I) . The geometric constraints provided by secondary interactions are reminiscent of blue copper proteins where a constrained geometry, or entatic state, allows for extremely rapid Cu(I)/Cu(II) electron-transfer self-exchange rates. Cu(H2 Tpy(NMes))Cl shows similar fast electron transfer (?10(5) ?m(-1) ?s(-1)) which is the same order of magnitude as biological systems.
Project description:Phosphine-stabilized germaborenes featuring an unprecedented Ge=B double bond with short B???Ge contacts of 1.886(2) (4) and 1.895(3)?Å (5) were synthesized starting from an intramolecular germylene-phosphine Lewis pair (1). After oxidative addition of boron trihalides BX3 (X=Cl, Br), the addition products were reduced with magnesium and catalytic amounts of anthracene to give the borylene derivatives in yields of 78?% (4) and 57?% (5). These halide-substituted germaborenes were characterized by single-crystal structure analysis, and the electronic structures were studied by quantum-chemical calculations. According to an NBO NRT analysis, the dominating Lewis structure contains a Ge=B double bond. The germaborenes undergo a reversible, photochemically initiated [2+2] cycloaddition with the phenyl moiety of a terphenyl substituent at room temperature, forming a complex heterocyclic structure with GeIV in a strongly distorted coordination environment.
Project description:The structure of the title compound, [Sn(2)Br(1.97)Cl(4.03)(OH)(2)(H(2)O)(2)]·2C(3)H(6)O, contains two hexa-coordinated Sn atoms bridged symmetrically by two hydroxide groups, with an inversion center in the middle of the planar Sn(2)O(2) ring, half of the mol-ecule being generated by inversion symmetry. The other sites of the distorted octa-hedral coordination geometry are occupied by halide atoms and water mol-ecules. The structure exhibits substitutional disorder of the halide atoms bonded to the Sn atom, with 0.672?(4) occupancy for Cl and 0.328?(4) for Br for each halide position. The compound crystallizes with two acetone mol-ecules, which are involved in intra- and inter-molecular O-H?O contacts. The water mol-ecules coordinated to the Sn atoms are also involved in O-H?O and O-H?X contacts, leading to a polymeric array along the a axis.
Project description:The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB catenane, in comparison to the acyclic XB receptor, due to the interlocked host's unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the catenane in competitive organic-aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared to the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (?(AX?X(-))(*) ? X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). The data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.
Project description:Dirhenium halide dianions received considerable attention in past decades due to the unusual metal-metal quadruple bond. The systematic structural evolution of dirhenium halide clusters has not been sufficiently studied and hence is not well-understood. In this work, we report an in-depth investigation on the structures and electronic properties of doubly charged dirhenium halide clusters Re<sub>2</sub>X<sub>8</sub><sup>2-</sup> (X?=?F, Cl, Br, I). Our computational efforts rely on the well-tested unbiased CALYPSO (Crystal structure AnaLYsis by Particle Swarm Optimization) method combined with density?functional?theory calculations. We find that all ground-state Re<sub>2</sub>X<sub>8</sub><sup>2-</sup> clusters have cube-like structures of D<sub>4h</sub> symmetry with two Re atoms encapsulated in halogen framework. The reasonable agreement between the simulated and experimental photoelectron spectrum of the Re<sub>2</sub>Cl<sub>8</sub><sup>2-</sup> cluster supports strongly the reliability of our computational strategy. The chemical bonding analysis reveals that the ? bond is the pivotal factor for the ground-state Re<sub>2</sub>X<sub>8</sub><sup>2-</sup> (X?=?F, Cl, Br, I) clusters to maintain D<sub>4h</sub> symmetric cube-like structures, and the enhanced stability of Re<sub>2</sub>Cl<sub>8</sub><sup>2-</sup> is mainly attributed to the chemical bonding of 5d orbital of Re atoms and 3p orbital of Cl atoms.
Project description:All-inorganic double perovskites (elpasolites) are a promising potential alternatives to lead halide perovskites in optoelectronic applications. Although halide mixing is a well-established strategy for band gap tuning, little is known about halide mixing and phase segregation phenomena in double perovskites. Here, we synthesize a wide range of single- and mixed-halide Cs2AgBiX6 (X = Cl, Br, and I) double perovskites using mechanosynthesis and probe their atomic-level microstructure using 133Cs solid-state MAS NMR. We show that mixed Cl/Br materials form pure phases for any Cl/Br ratio while Cl/I and Br/I mixing is only possible within a narrow range of halide ratios (<3 mol % I) and leads to a complex mixture of products for higher ratios. We characterize the optical properties of the resulting materials and show that halide mixing does not lead to an appreciable tunability of the PL emission. We find that iodide incorporation is particularly pernicious in that it quenches the PL emission intensity and radiative charge carrier lifetimes for iodide ratios as low as 0.3 mol %. Our study shows that solid-state NMR, in conjunction with optical spectroscopies, provides a comprehensive understanding of the structure-activity relationships, halide mixing, and phase segregation phenomena in Cs2AgBiX6 (X = Cl, Br, and I) double perovskites.