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1.
Zincocene and Dizincocene N‐Heterocyclic Carbene Complexes and Catalytic Hydrogenation of Imines and Ketones
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Dr. Phillip Jochmann Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8370-8378
The N‐heterocyclic carbene (NHC) adducts Zn(CpR)2(NHC)] (CpR=C5HMe4, C5H4SiMe3; NHC=ItBu, IDipp (Dipp=2,6‐diisopropylphenyl), IMes (Mes=mesityl), SIMes) were prepared and shown to be active catalysts for the hydrogenation of imines, whereas decamethylzincocene [ZnCp*2] is highly active for the hydrogenation of ketones in the presence of noncoordinating NHCs. The abnormal carbene complex [Zn(OCHPh2)2(aItBu)]2 was formed from spontaneous rearrangement of the ItBu ligand during incomplete hydrogenation of benzophenone. Two isolated ZnI adducts [Zn2Cp*2(NHC)] (NHC=ItBu, SIMes) are presented and characterized as weak adducts on the basis of 13C NMR spectroscopic and X‐ray diffraction experiments. A mechanistic proposal for the reduction of [ZnCp*2] with H2 to give [Zn2Cp*2] is discussed. 相似文献
2.
Amy L. Speelman Ba L. Tran Jeremy D. Erickson Monica Vasiliu David A. Dixon R. Morris Bullock 《Chemical science》2021,12(34):11495
Most ligand designs for reactions catalyzed by (NHC)Cu–H (NHC = N-heterocyclic carbene ligand) have focused on introducing steric bulk near the Cu center. Here, we evaluate the effect of remote ligand modification in a series of [(NHC)CuH]2 in which the para substituent (R) on the N-aryl groups of the NHC is Me, Et, tBu, OMe or Cl. Although the R group is distant (6 bonds away) from the reactive Cu center, the complexes have different spectroscopic signatures. Kinetics studies of the insertion of ketone, aldimine, alkyne, and unactivated α-olefin substrates reveal that Cu–H complexes with bulky or electron-rich R groups undergo faster substrate insertion. The predominant cause of this phenomenon is destabilization of the [(NHC)CuH]2 dimer relative to the (NHC)Cu–H monomer, resulting in faster formation of Cu–H monomer. These findings indicate that remote functionalization of NHCs is a compelling strategy for accelerating the rate of substrate insertion with Cu–H species.Remote modification of an N-heterocyclic carbene ligand with bulky or electron-rich groups in [(NHC)Cu(μ-H)]2 increases the rate of substrate insertion, which kinetics studies suggest arises from changes in the Cu–H monomer–dimer equilibrium. 相似文献
3.
The addition of [(L)4Ca(I)Mes] (Lewis base L=thf, Et2O) to mesityl copper(I) and the transmetalation reaction of mesityl copper(I) with activated calcium are suitable pathways for the synthesis of dimesityl cuprates(I) of calcium. However, the structures of the calcium cuprates(I) depend on the preparative procedure. The transmetalation reaction leads to the formation of [Mes‐Cu‐Mes]? anions whereas the addition yields dinuclear [(Mes‐Cu)2(μ‐Mes)]? anions. The solvent‐separated counterions are [Ca(thf)6]2+ and [(thf)5CaI]+, respectively. In contrast to these findings, the addition of [(L)4Ca(I)Mes] to mesityl copper(I) in an Et2O/toluene mixture led to formation of tetrameric solvent‐free iodocalcium dimesityl cuprate(I) [ICa(μ‐η1,η6‐Mes2Cu)]4, representing a rare example of a heavy Normant‐type organocuprate. 相似文献
4.
Reaction of the cyclodiphosphazane [(OC4H8N)P(μ‐N‐t‐Bu)2P(HN‐t‐Bu)] ( 1 ) with an equimolar quantity of diisopropyl azodicarboxylate afforded the phosphinimine product [(OC4H8N)P(μ‐N‐t‐Bu)2P=N‐t‐Bu)(N(CO2 ‐i‐Pr)NHCO2‐i‐Pr] ( 6 ) having a PIII‐N‐PV skeleton. Similar products [(t‐BuNH)P(μ‐N‐t‐Bu)2P=N‐t‐Bu)(N(CO2Et)NHCO2Et] ( 7 ) and [(CO2‐i‐Pr)HNN(CO2‐i‐Pr)](t‐BuN=P(μ‐N‐t‐Bu)2POCH2CMe2CH2O[P(μ‐N‐t‐Bu)2P=N‐t‐Bu)(N(CO2‐i‐Pr)NH(CO2‐i‐Pr)] ( 8 ) were spectroscopically characterized in the reaction of [(t‐BuNH)P‐N‐t‐Bu]2 ( 2 ) and [(t‐BuNH)P(μ‐N‐t‐Bu)2POCH2CMe2CH2OP(μ‐N‐t‐Bu)2P(NH‐t‐Bu)] ( 3 ) with diethyl‐ and diisopropyl azodicarboxylate, respectively. By contrast, the reaction of [(μ‐t‐BuN)P]2[O‐6‐t‐Bu‐4‐Me‐C6H2]2CH2 ( 4 ) and [(C5H10N)P‐μ‐N‐t‐Bu]2 ( 5 ) with diisopropyl azodicarboxylate afforded the mono‐ and bis‐oxidized compounds [(O)P(μ‐N‐t‐Bu)2P][O‐6‐t‐Bu‐4‐Me‐C6H2]2CH2 ( 9 ) and [(C5H10N)(O)P‐μ‐N‐t‐Bu]2 ( 10 ), respectively. Oxidative addition of o‐chloranil to 7 and its DIAD analogue [(t‐BuNH)P(μ‐N‐t‐Bu)2P=N‐t‐Bu)(N(CO2‐i‐Pr)NHCO2‐i‐Pr] ( 11 ) afforded [(C6Cl4‐1, 2‐O2)(t‐BuNH)P(μ‐N‐t‐Bu)2P=N‐t‐Bu)(N(CO2R)NHCO2R] [R = Et ( 12 ) and i‐Pr ( 13 )] containing tetra‐ and pentacoordinate PV atoms in the cyclodiphosphazane ring. The structures of 6 , 9 , 12 and 13 have been confirmed by X‐ray structure determination. For comparison, the X‐ray structure of the double cycloaddition product [(C6Cl4‐1, 2‐O2)(t‐BuNH)PN‐t‐Bu]2 ( 14 ), obtained from the reaction of 2 with two mole equivalents of o‐chloranil is also reported. 相似文献
5.
Süleyman Gülcemal 《应用有机金属化学》2012,26(5):246-251
Six new [RhBr(NHC)(cod)] (NHC = N‐heterocyclic carbene; cod = 1,5‐cyclooctadiene) type rhodium complexes ( 4–6 ) have been prepared by the reaction of [Rh(μ‐OMe)(cod)]2 with a series of corresponding imidazoli(in)ium bromides ( 1–3 ) bearing mesityl (Mes) or 2,4,6‐trimethylbenzyl (CH2Mes) substituents at N1 and N3 positions. They have been fully characterized by 1 H, 13 C and heteronuclear multiple quantum correlation NMR analyses, elemental analysis and mass spectroscopy. Complexes of type [(NHC)RhBr(CO)2] (NHC = imidazol‐2‐ylidene) ( 7b–9b ) were also synthesized to compare σ‐donor/π‐acceptor strength of NHC ligands. Transfer hydrogenation (TH) reaction of acetophenone has been comparatively studied by using complexes 4–6 as catalysts. The symmetrically CH2Mes‐substituted rhodium complex bearing a saturated NHC ligand ( 5a ) showed the highest catalytic activity for TH reaction. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
6.
Lee R. Collins Gabriele Hierlmeier Dr. Mary F. Mahon Dr. Ian M. Riddlestone Prof. Michael K. Whittlesey 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(8):3215-3218
The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P4. Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6‐MesDAC‐R)MR] (M=Zn, Cd; R=Et, Me; Mes=mesityl). These species were formed via the spectroscopically characterised intermediates [(6‐MesDAC)MR2], exhibiting barriers to migratory insertion which increase in the order MR2 = ZnEt2 < ZnMe2 < CdMe2. Compound [(6‐MesDAC‐Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent β‐H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M‐R, M‐H). 相似文献
7.
Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η5‐C5R5)M(NR′)2Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η5‐C5R5)M(NR′)2Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η5‐C5Me5)M(NtBu)2Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η5‐C5Me5)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η5‐C5Me5)M(O)2(CH3)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η5‐C5H5)W(NtBu)2(CH3)] and [(η5‐C5Me5)Mo(NtBu)2(CH3)] by HCl gas leads to [(η5‐C5H5)W(NtBu)Cl2(CH3)] 14 und [(η5‐C5Me5)Mo(NtBu)Cl2(CH3)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η5‐C5R5)M(NR′)Cl3] with MeLi. As pure substances only trimethyl compounds [(η5‐C5R5)M(NtBu)(CH3)3] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η5‐C5Me5)M(NtBu)(CHPh)(CH2Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η5‐C5Me5)M(NtBu)Cl3] with PhCH2MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]2— > [O]2— > [CHR]2— ? 2 [CH3]— > 2 [Cl]— emerges. 相似文献
8.
Dr. Evan A. Patrick Dr. Mark E. Bowden Dr. Jeremy D. Erickson Dr. R. Morris Bullock Dr. Ba L. Tran 《Angewandte Chemie (International ed. in English)》2023,62(30):e202304648
Mechanistic studies of substrate insertion into dimeric [(NHC)CuH]2 (NHC=N-heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu−H monomers in solution. Using single-crystal to single-crystal (SC-SC) transformations, we discovered a new pathway of stepwise insertion of CO2 into [(NHC)CuH]2 without complete dissociation of the dimer. The first CO2 insertion into dimeric [(IPr*OMe)CuH]2 (IPr*OMe=N,N′-bis(2,6-bis(diphenylmethyl)-4-methoxy-phenyl)imidazole-2-ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-H). A second CO2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu]2(μ-1,3-O2CH)(μ-1,1-O2CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent. 相似文献
9.
Matthew J. Evans Dr. Mathew D. Anker Ahmed Mouchfiq Dr. Matthias Lein Dr. J. Robin Fulton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(12):2606-2609
Addition of MesN3 (Mes=2,4,6-Me3C6H2) to germylene [(NONtBu)Ge] (NONtBu=O(SiMe2NtBu)2) ( 1 ) gives germanimine, [(NONtBu)Ge=NMes] ( 2 ). Compound 2 behaves as a metalloid, showing reactivity reminiscent of both transition metal-imido complexes, undergoing [2+2] addition with heterocumulenes and protic sources, as well as an activated diene, undergoing a [4+2] cycloaddition, or “metallo”-Diels–Alder, reaction. In the latter case, the diene includes the Ge=N bond and π-system of the Mes substituent, which is reactive towards dienophiles including benzaldehyde, benzophenone, styrene, and phenylacetylene. 相似文献
10.
Igor L. Fedushkin Prof. Dr. Anton N. Lukoyanov Markus Hummert Herbert Schumann Prof. Dr. 《无机化学与普通化学杂志》2008,634(2):357-361
At elevated temperatures, the aluminum complex [(dpp‐BIAN)AlI(Et2O)] ( 1 ) splits the C‐O bonds of diethyl ether and tetrahydrofurane yielding the dimeric alkoxides [(dpp‐BIAN)AlOEt]2 ( 2 ) and [(dpp‐BIAN)AlO(CH2)4I]2 ( 3 ), respectively. Already at ambient temperatures, a cleavage of the C‐O bond of THF is to observe in the reaction of 1 with CpNa in THF as confirmed by the formation of [(dpp‐BIAN)AlO(CH2)4C5H5]2 ( 4a ) and [(dpp‐BIAN)Al{O(CH2)4C5H5}(THF)] ( 4b ) in a molar ratio of 1:2. The reaction of 1 with t‐BuOK affords the monomeric alkoxide [(dpp‐BIAN)AlO‐t‐Bu(Et2O)] ( 5 ). Compounds 2 , 3 , and 4a/b were characterized by elemental analyses and IR spectra. Additionally, the structures of 2 and 3 were determined by single crystal X‐ray diffraction. 相似文献
11.
New Copper Complexes Containing Phosphaalkene Ligands. Molecular Structure of [Cu{P(Mes*)C(NMe2)2}2]BF4 (Mes* = 2,4,6‐tBu3C6H2) Reaction of equimolar amounts of the inversely polarized phosphaalkene tBuP=C(NMe2)2 ( 1a ) and copper(I) bromide or copper(I) iodide, respectively, affords complexes [Cu3X3{μ‐P(tBu)C(NMe2)2}3] ( 2 ) (X =Br) and ( 3 ) (X = I) as the formal result of the cyclotrimerization of a 1:1‐adduct. Treatment of 1a with [Cu(L)Cl] (L = PiPr3; SbiPr3) leads to the formation of compounds [CuCl(L){P(tBu)C(NMe2)2}] ( 4a ) (L = PiPr3) and ( 4b ) (L = SbiPr3), respectively. Reaction of [(MeCN)4Cu]BF4 with two equivalents of PhP=C(NMe2)2 ( 1b ) yields complex [Cu{P(Ph)C(NMe2)2}2]BF4 ( 5b ). Similarly, compounds [Cu{P(Aryl)C(NMe2)2}2]BF4 ( 5c (Aryl = Mes and 5d (Aryl = Mes*)) are obtained from ArylP=C(NMe2)2 ( 1c : Aryl = Mes; 1d : Mes*) and [(MeCN)4Cu]BF4 in the presence of SbiPr3. Complexes 2 , 3 , 4a , 4b , and 5b‐5d are characterized by means of elemental analyses and spectroscopy (1H‐, 13C{1H}‐, 31P{1H}‐NMR). The molecular structure of 5d is determined by X‐ray diffraction analysis. 相似文献
12.
Maotong Xu Andrew R. Jupp Douglas W. Stephan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3586-3590
The analogy of the reactivity of group 1 phosphides to that of FLPs is further demonstrated by reactions with CO, affording a new synthetic route to acyl‐phosphide anions. The reaction of [K(18‐crown‐6)][PtBu2] ( 1 ) with CO affords [(18‐crown‐6)K?THF2][Z‐tBuP=C(tBu)O] ( 2?THF2 ) as the major product, and the minor product [K6(18‐crown‐6)][(tBu2PCO)2]3 ( 3 ). Species 2 reacts with either BPh3 or additional CO to give [K(18‐crown‐6)][(Ph3B)tBuPC(tBu)O] ( 4 ) and [K(18‐crown‐6)][(OCtBu)2P] ( 5 ), respectively. The acyl‐phosphide anion 2 is thought to be formed by a photochemically induced radical process involving a transient species with triplet carbene character, prompting 1,2‐tert‐butyl group migration. A similar process is proposed for the subsequent reaction of 2 with CO to give 5 . 相似文献
13.
Normal‐to‐Abnormal NHC Rearrangement of AlIII,GaIII, and InIII Trialkyl Complexes: Scope,Mechanism, Reactivity Studies,and H2 Activation
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Dr. Gilles Schnee Prof. Olalla Nieto Faza Dr. David Specklin Dr. Béatrice Jacques Dr. Lydia Karmazin Prof. Richard Welter Prof. Carlos Silva López Dr. Samuel Dagorne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17959-17972
The present contribution reports experimental and theoretical mechanistic investigations on a normal‐to‐abnormal (C2‐to‐C4‐bonded) NHC rearrangement processes occurring with bulky group 13 metal NHC adducts, including the scope of such a reactivity for Al compounds. The sterically congested adducts (nItBu)MMe3 (nItBu=1,3‐di‐tert‐butylimidazol‐2‐ylidene; M=Al, Ga, In; 1 a – c ) readily rearrange to quantitatively afford the corresponding C4‐bonded complexes (aItBu)MMe3 ( 4 a – c ), a reaction that may be promoted by THF. Thorough experimental data and DFT calculations were performed on the nNHC‐to‐aNHC process converting the Al‐nNHC ( 1 a ) to its aNHC analogue 4 a . A nItBu/aItBu isomerization is proposed to account for the formation of the thermodynamic product 4 a through reaction of transient aItBu with THF–AlMe3. The reaction of benzophenone with (nItBu)AlMe3 afforded the zwitterionic species (aItBu)(CPh2‐O‐AlMe3) ( 6 ), reflecting the unusual reactivity that such bulky adducts may display. Interestingly, the nItBu/Al(iBu)3 Lewis pair behaves like a frustrated Lewis pair (FLP) since it readily reacts with H2 under mild conditions. This may open the way to future reactivity developments involving commonly used trialkylaluminum precursors. 相似文献
14.
Rare‐Earth‐Metal Methyl,Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand
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Dorothea Schädle Dr. Cäcilia Maichle‐Mössmer Dr. Christoph Schädle Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):662-670
The reaction of monomeric [(TptBu,Me)LuMe2] (TptBu,Me=tris(3‐Me‐5‐tBu‐pyrazolyl)borate) with primary aliphatic amines H2NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(TptBu,Me)LuMe(NHR)], the solid‐state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(TptBu,Me)LnMe({μ2‐Me}AlMe3)] (Ln=Y, Ho) reacted selectively and in high yield with H2NR, according to methane elimination, to afford heterobimetallic complexes: [(TptBu,Me)Ln({μ2‐Me}AlMe2)(μ2‐NR)] (Ln=Y, Ho). X‐ray structure analyses revealed that the monomeric alkylaluminum‐supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by 1H and 13C NMR spectroscopic studies at variable temperatures and 1H–89Y HSQC NMR spectroscopy. Treatment of [(TptBu,Me)LnMe(AlMe4)] with H2NtBu gave dimethyl compounds [(TptBu,Me)LnMe2] as minor side products for the mid‐sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative‐scale amounts of complexes [(TptBu,Me)LnMe2] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(TptBu,Me)LnMe(AlMe4)] with N,N,N′,N′‐tetramethylethylenediamine (tmeda). The solid‐state structures of [(TptBu,Me)HoMe(AlMe4)] and [(TptBu,Me)HoMe2] were analyzed by XRD. 相似文献
15.
Dr. Laura Rubio‐Pérez Dipl.‐Chem. Ramón Azpíroz Dr. Andrea Di Giuseppe Dr. Victor Polo Dr. Ricardo Castarlenas Prof. Jesús J. Pérez‐Torrente Prof. Luis A. Oro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15304-15314
A general regioselective rhodium‐catalyzed head‐to‐tail dimerization of terminal alkynes is presented. The presence of a pyridine ligand (py) in a Rh–N‐heterocyclic‐carbene (NHC) catalytic system not only dramatically switches the chemoselectivity from alkyne cyclotrimerization to dimerization but also enhances the catalytic activity. Several intermediates have been detected in the catalytic process, including the π‐alkyne‐coordinated RhI species [RhCl(NHC)(η2‐HC?CCH2Ph)(py)] ( 3 ) and [RhCl(NHC){η2‐C(tBu)?C(E)CH?CHtBu}(py)] ( 4 ) and the RhIII–hydride–alkynyl species [RhClH{? C?CSi(Me)3}(IPr)(py)2] ( 5 ). Computational DFT studies reveal an operational mechanism consisting of sequential alkyne C? H oxidative addition, alkyne insertion, and reductive elimination. A 2,1‐hydrometalation of the alkyne is the more favorable pathway in accordance with a head‐to‐tail selectivity. 相似文献
16.
tert‐Butyl(tert‐butoxy)zinc Hydroxides: Hybrid Models for Single‐Source Precursors of ZnO Nanocrystals
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Kamil Sokołowski Dr. Iwona Justyniak Dr. Wojciech Bury Dr. Justyna Grzonka Prof. Zbigniew Kaszkur Łukasz Mąkolski Michał Dutkiewicz Agnieszka Lewalska Elżbieta Krajewska Dominik Kubicki Dr. Katarzyna Wójcik Prof. Krzysztof J. Kurzydłowski Prof. Janusz Lewiński 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5488-5495
Alkylzinc alkoxides, [RZnOR′]4, have received much attention as efficient precursors of ZnO nanocrystals (NCs), and their “Zn4O4” heterocubane core has been regarded as a “preorganized ZnO”. A comprehensive investigation of the synthesis and characterization of a new family of tert‐butyl(tert‐butoxy)zinc hydroxides, [(tBu)4Zn4(μ3‐OtBu)x(μ3‐OH)4?x], as model single‐source precursors of ZnO NCs is reported. The direct reaction between well‐defined [tBuZnOH]6 ( 16 ) and [tBuZnOtBu]4 ( 24 ) in various molar ratios allows the isolation of new mixed cubane aggregates as crystalline solids in a high yield: [(tBu)4Zn4(μ3‐OtBu)3(μ3‐OH)] ( 3 ), [(tBu)4Zn4(μ3‐OtBu)2(μ3‐OH)2] ( 4 ), [(tBu)4Zn4(μ3‐OtBu)(μ3‐OH)3] ( 5 ). The resulting products were characterized in solution by 1H NMR and IR spectroscopy, and in the solid state by single‐crystal X‐ray diffraction. The thermal transformations of 2 – 5 were monitored by in situ variable‐temperature powder X‐ray diffraction and thermogravimetric measurements. The investigation showed that the Zn?OH groups appeared to be a desirable feature for the solid‐state synthesis of ZnO NCs that significantly decreased the decomposition temperature of crystalline precursors 3 – 5 . 相似文献
17.
Dr. Steffen Styra Michael Radius Dr. Eric Moos Dr. Angela Bihlmeier Prof. Dr. Frank Breher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9508-9512
The synthesis and characterisation of two aluminium diphosphamethanide complexes, [Al(tBu)2{κ2P,P′‐Mes*PCHPMes*}] ( 3 ) and [Al(C6F5)2{κ2P,P′‐Mes*PCHPMes*}] ( 4 ), and the silylated analogue, Mes*PCHP(SiMe3)Mes* ( 5 ), are reported. The aluminium complexes feature four‐membered PCPAl core structures consisting of diphosphaallyl ligands. The silylated phosphine 5 was found to be a valuable precursor for the synthesis of 4 as it cleanly reacts with the diaryl aluminium chloride [(C6F5)2AlCl]2. The aluminium complex 3 reacts with molecular dihydrogen at room temperature under formation of the acyclic σ2λ3,σ3λ3‐diphosphine Mes*PCHP(H)Mes* and the corresponding dialkyl aluminium hydride [tBu2AlH]3. Thus, 3 belongs to the family of so‐called hidden frustrated Lewis pairs. 相似文献
18.
Roxana M. Bîrzoi Dr. Delia Bugnariu Dr. Rafael Guerrero Gimeno Dr. Daniela Lungu Vera Zota Dr. Constantin Daniliuc Dr. Peter G. Jones Prof. Dr. Zoltán Benkõ Dr. László Könczöl László Nyulászi Prof. Dr. Rainer Bartsch Dr. Wolf‐W. du Mont Prof. Dr. Edgar Niecke Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(16):4843-4851
Deprotonation of aminophosphaalkenes (RMe2Si)2C?PN(H)(R′) (R=Me, iPr; R′=tBu, 1‐adamantyl (1‐Ada), 2,4,6‐tBu3C6H2 (Mes*)) followed by reactions of the corresponding Li salts Li[(RMe2Si)2C?P(M)(R′)] with one equivalent of the corresponding P‐chlorophosphaalkenes (RMe2Si)2C?PCl provides bisphosphaalkenes (2,4‐diphospha‐3‐azapentadienes) [(RMe2Si)2C?P]2NR′. The thermally unstable tert‐butyliminobisphosphaalkene [(Me3Si)2C?P]2NtBu ( 4 a ) undergoes isomerisation reactions by Me3Si‐group migration that lead to mixtures of four‐membered heterocyles, but in the presence of an excess amount of (Me3Si)2C?PCl, 4 a furnishes an azatriphosphabicyclohexene C3(SiMe3)5P3NtBu ( 5 ) that gave red single crystals. Compound 5 contains a diphosphirane ring condensed with an azatriphospholene system that exhibits an endocylic P?C double bond and an exocyclic ylidic P(+)? C(?)(SiMe3)2 unit. Using the bulkier iPrMe2Si substituents at three‐coordinated carbon leads to slightly enhanced thermal stability of 2,4‐diphospha‐3‐azapentadienes [(iPrMe2Si)2C?P]2NR′ (R′=tBu: 4 b ; R′=1‐Ada: 8 ). According to a low‐temperature crystal‐structure determination, 8 adopts a non‐planar structure with two distinctly differently oriented P?C sites, but 31P NMR spectra in solution exhibit singlet signals. 31P NMR spectra also reveal that bulky Mes* groups (Mes*=2,4,6‐tBu3C6H2) at the central imino function lead to mixtures of symmetric and unsymmetric rotamers, thus implying hindered rotation around the P? N bonds in persistent compounds [(RMe2Si)2C?P]2NMes* ( 11 a , 11 b ). DFT calculations for the parent molecule [(H3Si)2C?P]2NCH3 suggest that the non‐planar distortion of compound 8 will have steric grounds. 相似文献
19.
Schiff base supported mononuclear organotin(IV) complexes: Syntheses,structures and fluorescence cell imaging
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Richa Vinayak Dhritiman Dey Dipanjan Ghosh Dhrubajyoti Chattopadhyay Abhrajyoti Ghosh Hari Pada Nayek 《应用有机金属化学》2018,32(3)
Three mononuclear organotin(IV) complexes supported by Schiff bases have been synthesized. The complexes [(C6H5)2Sn(L)] ( 1 ), [(t‐Bu)2Sn(L)] ( 2 ) and [(t‐Bu)2Sn(L')] ( 3 ) (L, L' = deprotonated Schiff bases) were obtained in good yield by the reaction of Schiff bases H 2 L or H 2 L′ with corresponding diorganotin dichlorides respectively. All newly synthesized complexes were characterized by means of FT‐IR spectroscopy, elemental analysis and multinuclear (1H, 13C and 119Sn) NMR spectroscopy. In addition, single crystal X‐ray diffraction analyses were employed to establish the solid state molecular structures of these complexes. The structures of 1 – 3 reveal that all complexes are mononuclear with a five‐coordinated tin(IV) centre in it. The absorption and emission properties of all complexes have been investigated. Moreover, cytotoxicity and fluorescence cell imaging studies of theses complexes have been performed. 相似文献
20.
Vanadium(V) Oxo and Imido Calix[8]arene Complexes: Synthesis,Structural Studies,and Ethylene Homo/Copolymerisation Capability
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Prof. Dr. Carl Redshaw Dr. Mark J. Walton Dr. Darren S. Lee Chengying Jiang Dr. Mark R. J. Elsegood Dr. Kenji Michiue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5199-5210
Interaction of p‐tert‐butylcalix[8]areneH8 (L8H8) with [NaVO(OtBu)4] (formed in situ from VOCl3) afforded the complex [Na(NCMe)5][(VO)2L8H]?4 MeCN ( 1 ?4 MeCN). Increasing [NaVO(OtBu)4] to 4 equiv led to [Na(NCMe)6]2[(Na(VO)4L8)(Na(NCMe))3]2?10 MeCN ( 2 ?10 MeCN). With adventitious oxygen, reaction of 4 equiv of [VO(OtBu)3] with L8H8 afforded the alkali‐metal‐free complex [(VO)4L8(μ3‐O)2] ( 3 ); solvates 3 ?3 MeCN and 3 ?3 CH2Cl2 were isolated. For the lithium analogue, the order of addition had to be reversed such that lithium tert‐butoxide was added to L8H8 and then treated with 2 equiv of VOCl3; crystallisation afforded [(VO2)2Li6[L8](thf)2(OtBu)2(Et2O)2]?Et2O ( 4 ?Et2O). Upon extraction into acetonitrile, [Li(NCMe)4][(VO)2L8H]?8 MeCN ( 5 ?8 MeCN) was formed. Use of the imido precursors [V(NtBu)(OtBu)3] and [V(Np‐tolyl)(OtBu)3] and L8H8, afforded [tBuNH3][{V(p‐tolylN)}2L8H]?3 1/2 MeCN ( 6 ?3 1/2 MeCN). The molecular structures of 1 to 6 are reported. Complexes 1 , 3 , and 4 were screened as precatalysts for the polymerisation of ethylene in the presence of cocatalysts at various temperatures and for the copolymerisation of ethylene with propylene. Activities as high as 136 000 g (mmol(V) h)?1 were sometimes achieved; higher molecular weight polymers could be obtained versus the benchmark [VO(OEt)Cl2]. For copolymerisation, incorporation of propylene was 7.1–10.9 mol % (compare 10 mol % for [VO(OEt)Cl2]), although catalytic activities were lower than [VO(OEt)Cl2]. 相似文献