Facile construction of novel organolanthanide square-planar macrocycles through addition of carbodiimide to an amino group

The reactivity of lanthanocene derivatives containing the p-aminothiophenolate ligand towards carbodiimide was examined. Reaction of Cp2Ln(p-SC6H4NH2)(THF) with RN=C=NR in THF at room temperature gave four novel organolanthanide guanidinate complexes [Cp2Ln(p-SC6H4N(H)C(NHR)=NR)]4 (R = iPr, Ln = Yb (1a), Er (2a); R = Cy, Ln = Yb (2a), Er (2b)), formed by the addition of the C[double bond, length as m-dash]N double bonds of the carbodiimide molecule to the para-position amino group. Their unique square-planar macrocycle structures have been determined through X-ray single-crystal diffraction analysis. This result provides a potential method for the construction of organolanthanide macrocycles.     

Reactivity of organolanthanide and organolithium complexes containing the guanidinate ligands toward isocyanate or carbodiimide: synthesis and crystal structures

The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogen to yield the lanthanocene guanidinate complexes [(C5H5)2Ln(mu-eta1:eta2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatment of phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(mu-Gua) bond to yield the corresponding insertion products [(C5H5)2Ln(mu-eta1:eta2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er (4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligand bond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2 under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2. As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novel organolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln = Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis.     

Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds

Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO…HNO, HCOOH…HNO, HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F. The geometric structures and vibrational frequencies of these six complexes at the MP2/6-31+G(d,p), MP2/6-311++G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in complexes HCHO…HNO and HCOOH…HNO the N-H bond is strongly contracted and N-H…O blue-shifted hydrogen bonds are observed. While in complexes HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F, the N-H bond is elongated and N-H…O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the X-H bond length in the X-H…Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribution, rehybridization and structural reorganization. Among them hyperconjugation has the effect of elongating the X-H bond, and the other three factors belong to the bond shortening effects. In complexes HCHO…HNO and HCOOH…HNO, the shortening effects dominate which lead to the blue shift of the N-H stretching frequencies. In complexes HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F where elongating effects are dominant, the N-H…O hydrogen bonds are red-shifted.     

Hydrogen bonding and covalent effects in binding of cisplatin to purine bases: ab initio and atoms in molecules studies

Ab initio and density functional calculations are employed to investigate the role of hydrogen bonding in the binding of cisplatin to the purine bases guanine and adenine. Through the use of the theory of atoms in molecules (AIM), it is shown that hydrogen bonds are ubiquitous in such systems, with N-H...N and N-H...Cl interactions present in addition to the expected N-H...O. This in turn means that the known stability of cisplatin-guanine complexes cannot be ascribed solely to hydrogen bonding and allows decomposition of total binding energy into contributions from covalent and hydrogen bonds. To do so, a new method for predicting hydrogen bond energies from bond critical point properties is proposed, employing partial least-squares analysis to remove the family dependence of simple models. Still more hydrogen bond motifs are found in bifunctional complexes of the general type purine-[Pt(NH(3))(2)](2+)-purine, including purine...purine contacts, though again the energetics of these are insufficient to explain the observed trends in stability. Finally, the effect of platination on the pairing of guanine with cytosine is studied in a similar manner, revealing large redistributions of hydrogen bonding but surprisingly small overall changes in pairing energy.     

Systematic ab initio study of 15N-15N and 15N-1H spin-spin coupling constants across N-H+-N hydrogen bonds: predicting N-N and N-H coupling constants and relating them to hydrogen bond type

A systematic ab initio EOM-CCSD study of 15N-15N and 15N-1H spin-spin coupling constants has been carried out for a series of complexes formed from 11 nitrogen bases with experimentally measured proton affinities. When these complexes are arranged in order of increasing proton affinity of the proton-acceptor base and, for each proton acceptor, increasing order of proton affinity of the protonated N-H donor, trends in distances and signs of coupling constants are evident that are indicative of the nature of the hydrogen bond. All two-bond spin-spin coupling constants (2hJ(N-N)) are positive and decrease as the N-N distance increases. All one-bond N-H coupling constants (1J(N-H)) are negative (1K(N-H) are positive). 1J(N-H) is related to the N-H distance and the hybridization of the donor N atom. One-bond H...N coupling constants (1hJ(H-N)) are positive (1hK(H-N) are negative) for traditional hydrogen bonds, but 1hJ(H-N) becomes negative when the hydrogen bond acquires sufficient proton-shared character. The N-N and H...N distances at which 1hJ(H-N) changes sign are approximately 2.71 and 1.62 A, respectively. Predictions are made of the values of 2hJ(N-N) and 1J(N-H), and the signs of 1hJ(H-N), for those complexes that are too large for EOM-CCSD calculations.     

Theoretical investigation of in-plane hydrogen-bonded complexes of ammonia with partially substituted fluorobenzenes

Systematic investigation of in-plane hydrogen-bonded complexes of ammonia with partially substituted fluorobenzenes has revealed that fluorobenzene, difluorobenzene, and trifluorobenzene favor formation of cyclic complexes with a C-H...N-H...F-C binding motif. On the other hand, tetrafluorobenzene and pentafluorobenzene favor formation of linear C-H...N hydrogen-bonded complexes. The complete absence of exclusively linear N-H...F hydrogen-bonded complexes for the entire series indicates that C-F bond in fluorobenzenes is a reluctant hydrogen-bond acceptor. However, fluorine does hydrogen bond when cooperatively stabilized with C-H...N hydrogen bonds for the lower fluoro analogues. The propensity of fluorobenzenes to adapt to the C-H...N-H...F-C binding motif decreases with the progressive fluorination of the benzene ring and disappears completely when benzene ring is substituted with five or more fluorine atoms.     

The gold-ammonia bonding patterns of neutral and charged complexes Au m 0+/-1-(NH3)n. I. Bonding and charge alternation

The gold-ammonia bonding patterns of the complexes which are formed between the ammonia clusters (NH(3))(1< or =n< or =3) and gold clusters of different sizes that range from one gold atom to the tri-, tetra-, and 20-nanogold clusters are governed by two basic and fundamentally different ingredients: the anchoring Au-N bond and the nonconventional N-H...Au hydrogen bond. The latter resembles, by all features, a conventional hydrogen bond and is formed between a typical conventional proton donor N-H group and the gold cluster that behaves as a nonconventional proton acceptor. We provide strong computational evidence that the gold-ammonia bonding patterns exhibit distinct characteristics as the Z charge state of the gold cluster varies within Z=0,+/-1. The analysis of these bonding patterns and their effects on the N-H...N H-bonded ammonia clusters are the subject of this paper.     

Influence of substituents on the strength of aryl C-H...anion hydrogen bonds

[structure: see text]When electron-withdrawing substituents are present, aryl C-H groups become powerful hydrogen bond donors, forming stronger complexes than obtained with conventional O-H and N-H groups.     

含取代茚基配体稀土金属有机化合物的合成及表征

采用Schlenk技术,在干燥纯氩气保护下,用无水三氯化稀土LnCl3与等摩尔的2-苯基茚(2-Phlnd)锂盐在THF中反应,得到8种未见报道的稀土金属有机配合物：(2-PhInd)Lncl2。所有配合物都经元素分析、IR和MS表征,并推测出其可能的分子结构。     

Ab initio study of ternary complexes X:(HCNH)(+):Z with X, Z = NCH, CNH, FH, ClH, and FCl: diminutive cooperative effects on structures, binding energies, and spin-spin coupling constants across hydrogen bonds

Ab initio calculations have been performed on a series of complexes in which (HCNH)(+) is the proton donor and CNH, NCH, FH, ClH, and FCl (molecules X and Z) are the proton acceptors in binary complexes X:HCNH(+) and HCNH(+):Z, and ternary complexes X:HCNH(+):Z. These complexes are stabilized by C-H(+)···A and N-H(+)···A hydrogen bonds, where A is the electron-pair donor atom of molecules X and Z. Binding energies of the ternary complexes are less than the sum of the binding energies of the corresponding binary complexes. In general, as the binding energy of the binary complex increases, the diminutive cooperative effect increases. The structures of these complexes, data from the AIM analyses, and coupling constants (1)J(N-H), (1h)J(H-A), and (2h)J(N-A) for the N-H(+)···A hydrogen bonds, and (1)J(C-H), (1h)J(H-A), and (2h)J(C-A) for the C-H(+)···A hydrogen bonds provide convincing evidence of diminutive cooperative effects in these ternary complexes. In particular, the symmetric N···H(+)···N hydrogen bond in HCNH(+):NCH looses proton-shared character in the ternary complexes X:HCNH(+):NCH, while the proton-shared character of the C···H(+)···C hydrogen bond in HNC:HCNH(+) decreases in the ternary complexes HNC:HCNH(+):Z and eventually becomes a traditional hydrogen bond as the strength of the HCNH(+)···Z interaction increases.     

Studies on organolanthanide complexes: XII. Synthesis,identification and reactivity of organolanthanide and -yttrium chlorides with the chelating 1,1′-(3-oxa-pentamethylene)dicyclopentadienyl ligand

Seven new 1,1′-(3-oxa-pentamethylene0dicyclopentadienyl lanthanide and yttrium chlorides, (C₅H₄CH₂CH₂OCH₂CH₂C₅H₄)LnCl(Ln = Nd, Gd, Ho, Er, Yb, Lu and Y) were synthesized by using 1,1′-(3-oxa-pentamethylene)biscyclopentadienyl as ligand. Disproportionation of xicyclopentadienyl neodymium chloride is thus succesfully prevented, and a stable early lanthanocene chloride is obtained. All seven complexes are unsolvated monomers, containing an intramolecular coordination bond. Their structures were verified by elemental analyses, and IR, MS, XPS, ¹H NMR and ¹³C NMR spectroscopy. They are readily soluble in various solvents and more stable towards air and moisture than other related complexes without an intramolecular coordination bond. The complex/NaH system hydrogenates 1-hexane catalytically in hydrogen.     

Synthesis and Characterization of Ethylthioethylcyclopenta-dienyl Organolanthanide Complexes:Cp_2~(Th)LnCl(Ln=Gd,Dy),Cp_2LnCp~(Th)(Ln=Yb,Sm,Dy,Y) and Cp~(Th)ErCl_2·2THF

Introduction Functional substituted cyclopentadienyl organolan-thanide complexes continue to attract considerable at-tention because these donor-functionalized side chains can increase the stability of highly reactive organolan-thanide complexes by forming the additional in-tramolecular chelating coordination with the central metal, and for early lanthanide complexes, the enhanced stability offers the opportunity to explore the reactivity of the remaining ligands.1-4 In addition, the in-tramol…     

桥联二芴基稀土氯化物的合成及表征

用二（9－芴基）二甲基硅烷（Me2SiFlu2）的双锂盐与三氯稀土在室下反应合成了5个通式为Me2SiFlu2LnCl(Ln=Yb,Sm,La,Pr,Nd）的桥联二芴基稀土氯化物，所有配合物均经元素分析、IR，MS和^1H NMR表征。     

N-H bond activation by palladium(ii) and copper(i) complexes featuring a reactive bidentate PN-ligand

The first examples of reactivity at the backbone of a bidentate PN-ligand L1H relevant to N-H activation are described, leading to novel Pd(II) and Cu(I) amido complexes. Activation of the PN-ligand backbone led to selective dearomatization of the pyridyl ring structure. In the case of Pd(II), the intermediate could be efficiently stabilized using PMe(3). Selective N-H bond cleavage of e.g. trifluorosulfonylamide resulted in facile formation of mononuclear metal-amido species 2 and 4, which have been crystallographically characterized. Hydrogen-bonding dimerization is observed in these solid state structures. The results obtained with these structurally versatile and reactive scaffolds likely open up new avenues in cooperative catalysis.     

Different sites of insertion in the reaction of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] (R = H or Me): N-H vs. Re-N

The reactions of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] complexes lead to R'NCO insertion into the Re-N bond (for R = Me) or the N-H bond (R = H).     

An ab initio study of cooperative effects in ternary complexes X:CNH:Z with X, Z = CNH, FH, ClH, FCl, and HLi: structures, binding energies, and spin-spin coupling constants across intermolecular bonds

A systematic ab initio investigation has been carried out to determine the structures, binding energies, and spin-spin coupling constants of ternary complexes X:CNH:Z and corresponding binary complexes X:CNH and CNH:Z, for X, Z = CNH, FH, ClH, FCl, and HLi. The enhanced binding energies of ternary complexes X:CNH:Z for fixed X as a function of Z decrease in the same order as the binding energies of the binary complexes CNH:Z. In contrast, the enhanced binding energies of the ternary complexes for fixed Z as a function of X do not decrease in the same order as the binding energies of the binary complexes X:CNH, a consequence of the increased stabilities of ternary complexes FCl:CNH:Z due to very strong chlorine-shared halogen bonds. For complexes in which the X···CNH interaction is a D-H···C hydrogen bond for D-H the proton-donor group (N-H, F-H, or Cl-H), spin-spin coupling constants (1)J(D-H) and (2h)J(D-C) in ternary complexes X:CNH:Z decrease in absolute value as the binding energies of binary complexes CNH:Z and the enhanced binding energies of the ternary complexes for fixed X as a function of Z also decrease. However, (2X)J(F-C) increases as the enhanced binding energies of the ternary complexes FCl:CNH:Z decrease, a consequence of the nature of the chlorine-shared halogen bond. The one-bond coupling constants (1)J(N-H) for the CNH···Z interaction in ternary complexes vary significantly, depending on the nature of the X···CNH interaction. The largest values of (1)J(N-H) are found for ternary complexes with FCl as X. Two-bond coupling constants (2h)J(N-A) for A the proton-acceptor atom of Z, and (2d)J(N-H) decrease in absolute value in the order of decreasing enhancement energies of ternary complexes X:CNH:Z for fixed Z as a function of X.     

Cationic ruthenium(II) catalysts for oxidative C-H/N-H bond functionalizations of anilines with removable directing group: synthesis of indoles in water

Cationic ruthenium(II) complexes enabled oxidative C-H bond functionalizations with anilines bearing removable directing groups. The C-H/N-H bond cleavages occurred most efficiently in water as a sustainable solvent and provided general access to various bioactive indoles. Mechanistic studies provided strong support for a novel reaction manifold.     

Synthesis,Structure and Reactivity of Lanthanocene Complexes

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Photochemistry of hydrogen bonded heterocycles probed by photodissociation experiments and ab initio methods

In this perspective article, we focus on the photochemistry of five-membered nitrogen containing heterocycles (pyrrole, imidazole and pyrazole) in clusters. These heterocycles represent paradigmatic structures for larger biologically active heterocyclic molecules and complexes. The dimers of the three molecules are also archetypes of different bonding patterns: N-H···π interaction, N-H···N hydrogen bond and double hydrogen bond. We briefly review available data on photochemistry of the title molecules in the gas phase, but primarily we focus on the new reaction channels opened upon the complexation with other heterocycles or solvent molecules. Based on ab initio calculations we discuss various possible reactions in the excited states of the clusters: (1) hydrogen dissociation, (2) hydrogen transfer between the heterocyclic units, (3) molecular ring distortion, and (4) coupled electron-proton transfer. The increasing photostability with complexity of the system can be inferred from experiments with photodissociation in these clusters. A unified view on photoinduced processes in five-membered N-heterocycles is provided. We show that even though different deactivation channels are energetically possible for the complexed heterocycles, in most cases the major result is a fast reconstruction of the ground state. The complexed or solvated heterocycles are thus inherently photostable although the stability can in principle be achieved via different reaction routes.     

Recent advances in reaction of organolanthanides containing the N−H bonds with unsaturated organic small molecules

This article is intended to provide an overview on recent progress in the reaction chemistry of organolanthanide complexes with the nitrogen–hydrogen bonds toward a series of unsaturated organic small molecules. The synthesis, stoichiometric and catalytic reactions of these complexes are described.