共查询到20条相似文献,搜索用时 15 毫秒
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Dr. Nicolas Popoff Dr. Jeff Espinas Dr. Jérémie Pelletier Benoît Macqueron Dr. Kai C. Szeto Olivier Boyron Dr. Christophe Boisson Dr. Iker Del Rosal Dr. Laurent Maron Dr. Aimery De Mallmann Dr. Régis M. Gauvin Dr. Mostafa Taoufik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):964-973
Homoleptic benzyl derivatives of titanium and zirconium have been grafted onto silica that was dehydroxylated at 200 and 700 °C, thereby affording bi‐grafted and mono‐grafted single‐site species, respectively, as shown by a combination of experimental techniques (IR, MAS NMR, EXAFS, and elemental analysis) and theoretical calculations. Marked differences between these compounds and their neopentyl analogues are discussed and rationalized by using DFT. These differences were assigned to the selectivity of the grafting process, which, depending on the structure of the molecular precursors, led to different outcomes in terms of the mono‐ versus bi‐grafted species for the same surface concentration of silanol species. The benzylzirconium derivatives were active towards ethylene polymerization in the absence of an activator and the bi‐grafted species displayed higher activity than their mono‐grafted analogues. In contrast, the benzyltitanium and neopentylzirconium counterparts were not active under similar reaction conditions. 相似文献
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Quantum-chemical calculations with DFT (BP86) and ab initio methods (MP2, SCS-MP2) were carried out for protonated and diprotonated compounds N-H(+) and N-(H(+))(2) and for the complexes N-BH(3), N-(BH(3))(2), N-CO(2), N-(CO(2))(2), N-W(CO)(5), N-Ni(CO)(3) and N-Ni(CO)(2) where N=C(PH(3))(2) (1), C(PMe(3))(2) (2), C(PPh(3))(2) (3), C(PPh(3))(CO) (4), C(CO)(2) (5), C(NHC(H))(2) (6), C(NHC(Me))(2) (7) (Me(2)N)(2)C==C==C(NMe(2))(2) (8) and NHC (9) (NHC(H)=N-heterocyclic carbene, NHC(Me)=N-substituted N-heterocyclic carbene). Compounds 1-4 and 6-9 are very strong electron donors, and this is manifested in calculated protonation energies that reach values of up to 300 kcal mol(-1) for 7 and in very high bond strengths of the donor-acceptor complexes. The electronic structure of the compounds was analyzed with charge- and energy-partitioning methods. The calculations show that the experimentally known compounds 2-5 and 8 chemically behave like molecules L(2)C which have two L-->C donor-acceptor bonds and a carbon atom with two electron lone pairs. The behavior is not directly obvious when the linear structures of carbon suboxide and tetraaminoallenes are considered. They only come to the fore on reaction with strong electron-pair acceptors. The calculations predict that single and double protonation of 5 and 8 take place at the central carbon atom, where the negative charge increases upon subsequent protonation. The hitherto experimentally unknown carbodicarbenes 6 and 7 are predicted to be even stronger Lewis bases than the carbodiphosphoranes 1-3. 相似文献
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V. V. Kanazhevskii V. P. Shmachkova N. S. Kotsarenko V. N. Kolomiichuk D. I. Kochubei 《Journal of Structural Chemistry》2006,47(3):453-457
EXAFS and SAXS were used for structure elucidation of zirconium butoxide complexes in n-butanol at concentrations from 0.3 g to 0.015 g ZrO2 in 1 ml. The basic structural unit of the complex is a tetramer. It has two equal sides with zirconium atoms linked by double oxygen bridges and with zirconium-zirconium distances of 3.5 Å. The other sides in the tetramer are 3.3 Å and 3.9 Å. This difference in bond lengths is explained by the different numbers of double or single ligand bridges between zirconium atoms. The tetramers are apt to undergo oligomerization to form particles with a diameter of 80 Å in solution. 相似文献
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Herrmann H Fillol JL Wadepohl H Gade LH 《Angewandte Chemie (International ed. in English)》2007,46(44):8426-8430
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Pierrefixe SC Poater J Im C Bickelhaupt FM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(23):6901-6911
Silicon in [Cl? SiH3? Cl]? is hypervalent, whereas carbon in [Cl? CH3? Cl]? is not. We have recently shown how this can be understood in terms of the ball‐in‐a‐box model, according to which silicon fits perfectly into the box that is constituted by the five substituents, whereas carbon is too small and, in a sense, “drops to the bottom” of the box. But how does carbon acquire hypervalency in the isostructural and isoelectronic noble gas (Ng)/methyl cation complexes [Ng? CH3? Ng]+ (Ng=He and Ne), which feature a delocalized D3h‐symmetric structure with two equivalent C? Ng bonds? From Ng=Ar onwards, the [Ng? CH3? Ng]+ complex again acquires a propensity to localize one of its axial C? Ng bonds and to largely break the other one, and this propensity increases in the order Ng=Ar3Ng+ and, for comparison, CH3Ng+, NgHNg+, and NgH+. It appears that, at variance with [Cl? CH3? Cl]?, the carbon atom in [Ng? CH3? Ng]+ can no longer be considered as a ball in a box of the five substituents. 相似文献
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Zou R Li QS Xie Y King RB Schaefer HF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(35):11149-11157
The iron trifluorophosphane complexes [Fe(PF(3))(n)] (n=4, 5), [Fe(2)(PF(3))(n)] (n=8, 9), [H(2)Fe(PF(3))(4)], and [Fe(2)(PF(2))(2)(PF(3))(6)] have been studied by density functional theory. The lowest energy structures of [Fe(PF(3))(4)] and [Fe(PF(3))(5)] are a triplet tetrahedron and a singlet trigonal bipyramid, respectively. Both cis and trans octahedral structures were found for [H(2)Fe(PF(3))(4)] with the cis isomer lying lower in energy by approximately 10 kcal mol(-1). The lowest energy structure for [Fe(2)(PF(3))(8)] has two [Fe(PF(3))(4)] units linked only by an iron-iron bond of length 2.505 A consistent with the formal Fe=Fe double bond required to give both iron atoms the favored 18-electron configuration. In the lowest energy structure for [Fe(2)(PF(3))(9)] one of the iron atoms has inserted into a P-F bond of one of the PF(3) ligands to give a structure [(F(3)P)(4)Fe<--PF(2)Fe(F)(PF(3))(4)] with a bridging PF(2) group and a direct Fe-F bond. A bridging PF(3) group is found in a considerably higher energy [Fe(2)(PF(3))(9)] structure at approximately 30 kcal mol(-1) above the global minimum. However, this bridging PF(3) group keeps the two iron atoms too far apart (approximately 4 A) for the direct iron-iron bond required to give the iron atoms the favored 18-electron configuration. The preferred structure for [Fe(2)(PF(2))(2)(PF(3))(6)] has a bridging PF(2) group, as expected. However, this bridging PF(2) group bonds to one of the iron atoms through an P-Fe covalent bond and to the other iron through an F-->Fe dative bond, leaving an uncomplexed phosphorus lone pair. 相似文献
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A series of titanium and zirconium complexes based on aminoiminophosphorane ligands [Ph2P(Nt‐Bu)(NR)]2MCl2 ( 4 , M = Ti, R = Ph; 5 , M = Zr, R = Ph; 6 , M = Ti, R = SiMe3; 7 , M = Zr, R = SiMe3) have been synthesized by the reaction of the ligands with TiCl4 and ZrCl4. The structure of complex 4 has been determined by X‐ray crystallography. The observed very weak interaction between Ti and P suggests partial π‐electron delocalization through both Ti and P. The complexes 4–7 are inactive for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) or i‐Bu3Al–Ph3CB(C6F5)4 under atmospheric pressure, and is probably the result of low monomer ethylene concentration and steric congestion around the central metal. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
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Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands
Martin Haehnel Sven Hansen Dr. Anke Spannenberg Dr. Perdita Arndt Dr. Torsten Beweries Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10546-10553
A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph2P‐N‐PPh2 at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine ( 1 ) to [(Cp2TiCl)2] (Cp=η5‐cyclopentadienyl) generated [Cp2Ti(Cl)P(Ph2)N(H)PPh2] ( 2 ). The heterometallacyclic complex [Cp2Ti(κ2‐P,P‐Ph2P‐N‐PPh2)] ( 3 Ti ) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp2Ti(η2‐Me3SiC2SiMe3)] with the amine 1 . Reactions of the lithium amide [(thf)3Li{N(PPh2)2}] with [Cp2MCl2] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp2M(Cl){κ2‐N,P‐N(PPh2)2}] ( 4 Zr and 4 Hf ). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp2Zr(κ2‐P,P‐Ph2P‐N‐PPh2)] ( 3 Zr ). Complexes 2 , 3 Ti , 4 Hf , and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations. 相似文献
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Ostapowicz TG Hölscher M Leitner W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(37):10329-10338
Catalytic carboxylation reactions that use CO(2) as a C1 building block are still among the 'dream reactions' of molecular catalysis. To obtain a deeper insight into the factors that control the fundamental steps of potential catalytic cycles, we performed a detailed computational study of the insertion reaction of CO(2) into rhodium-alkyl bonds. The minima and transition-state geometries for 38 pincer-type complexes were characterized and the according energies for the C-C bond-forming step were determined. The electronic properties of the Rh-alkyl bond were found to be more important for the magnitude of the activation barrier than the interaction between rhodium and CO(2). The charge of the alkyl-chain carbon atom, as well as agostic and orbital interactions with the rhodium, exhibit the most pronounced influence on the energy of the transition states for the CO(2) insertion reaction. By varying the backbone and the donor groups of the pincer ligand those properties can be tuned over a very broad range. Thus, it is possible to match the electronic and steric properties with the fundamental requirements of the CO(2) insertion into rhodium-alkyl bonds of the ligand framework. 相似文献
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Elizabeth A. Jacobs Anna Fuller Simon J. Coles Graham J. Tizzard Joseph A. Wright Simon J. Lancaster 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(28):8647-8658
Treatment of Me2S ? B(C6F5)nH3?n (n=1 or 2) with ammonia yields the corresponding adducts. H3N ? B(C6F5)H2 dimerises in the solid state through N? H???H? B dihydrogen interactions. The adducts can be deprotonated to give lithium amidoboranes Li[NH2B(C6F5)nH3?n]. Reaction of the n=2 reagent with [Cp2ZrCl2] leads to disubstitution, but [Cp2Zr{NH2B(C6F5)2H}2] is in equilibrium with the product of β‐hydride elimination [Cp2Zr(H){NH2B(C6F5)2H}], which proves to be the major isolated solid. The analogous reaction with [Cp2HfCl2] gives a mixture of [Cp2Hf{NH2B(C6F5)2H}2] and the N? H activation product [Cp2Hf{NHB(C6F5)2H}]. [Cp2Zr{NH2B(C6F5)2H}2] ? PhMe and [Cp2Hf{NH2B(C6F5)2H}2] ? 4(thf) exhibit β‐B‐agostic chelate bonding of one of the two amidoborane ligands in the solid state. The agostic hydride is invariably coordinated to the outside of the metallocene wedge. Exceptionally, [Cp2Hf{NH2B(C6F5)2H}2] ? PhMe has a structure in which the two amidoborane ligands adopt an intermediate coordination mode, in which neither is definitively agostic. [Cp2Hf{NHB(C6F5)2H}] has a formally dianionic imidoborane ligand chelating through an agostic interaction, but the bond‐length distribution suggests a contribution from a zwitterionic amidoborane resonance structure. Treatment of the zwitterions [Cp2MMe(μ‐Me)B(C6F5)3] (M=Zr, Hf) with Li[NH2B(C6F5)nH3?n] (n=2) results in [Cp2MMe{NH2B(C6F5)2H}] complexes, for which the spectroscopic data, particularly 1J(B,H), again suggest β‐B‐agostic interactions. The reactions proceed similarly for the structurally encumbered [Cp′′2ZrMe(μ‐Me)B(C6F5)3] precursor (Cp′′=1,3‐C5H3(SiMe3)2, n=1 or 2) to give [Cp′′2ZrMe{NH2B(C6F5)nH3?n}], both of which have been structurally characterised and show chelating, agostic amidoborane coordination. In contrast, the analogous hafnium chemistry leads to the recovery of [Cp′′2HfMe2] and the formation of Li[HB(C6F5)3] through hydride abstraction. 相似文献