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1.
Akihiro Yoshinari Akira Tazawa Prof. Dr. Shigeki Kuwata Prof. Dr. Takao Ikariya 《化学:亚洲杂志》2012,7(6):1417-1425
A new metal–ligand bifunctional, pincer‐type ruthenium complex [RuCl( L1‐H2 )(PPh3)2]Cl ( 1 ; L1‐H2 =2,6‐bis(5‐tert‐butyl‐1H‐pyrazol‐3‐yl)pyridine) featuring two proton‐delivering pyrazole arms has been synthesized. Complex 1 , derived from [RuCl2(PPh3)3] with L1‐H2 , underwent reversible deprotonation with potassium carbonate to afford the pyrazolato–pyrazole complex [RuCl(L1‐H)(PPh3)2] ( 2 ). Further deprotonation of 1 and 2 with potassium hexamethyldisilazide in methanol resulted in the formation of the bis(pyrazolato) complex [Ru(L1)(MeOH)(PPh3)2] ( 3 ). Complex 3 smoothly reacted with dioxygen and dinitrogen to give the side‐on peroxo complex [Ru(L1)(O2)(PPh3)2] ( 4 ) and end‐on dinitrogen complex [Ru(L1)(N2)(PPh3)2] ( 5 ), respectively. On the other hand, the reaction of [RuCl2(PPh3)3] with less hindered 2,6‐di(1H‐pyrazol‐3‐yl)pyridine ( L3‐H2 ) led to the formation of the dinuclear complex [{RuCl2(PPh3)2}2(μ2‐ L3‐H2 )2] ( 6 ), in which the pyrazole‐based ligand adopted a tautomeric form different from L1‐H2 in 1 and the central pyridine remained uncoordinated. The detailed structures of 1 , 2 , 3 , 3.MeOH , 4 , 5 , 6 were determined by X‐ray crystallography. 相似文献
2.
Indre Thiel Dr. Haijun Jiao Dr. Anke Spannenberg Dr. Marko Hapke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(7):2548-2554
CpCoI‐olefin‐phosphite and CpCoI‐bisphosphite complexes were systematically prepared and their reactivity in [2+2+2] cycloaddition reactions compared with highly active [CpCo(H2C?CHSiMe3)2] ( 1 ). Whereas 1 is an excellent precursor for the synthesis of [CpCo(olefin)(phosphite)] complexes ( 2 a – f ), [CpCo(phosphite)2] complexes ( 3 a – e ) were prepared photochemically from [CpCo(cod)]. The complexes were evaluated in the cyclotrimerization reaction of diynes with nitriles yielding pyridines. For [CpCo(olefin)(phosphite)], as well as some of the [CpCo(phosphite)2] complexes, reaction temperatures as low as 50 °C were sufficient to perform the cycloaddition reaction. A direct comparison showed that the order of reactivity for the complex ligands was olefin2>olefin/phosphite>phosphites2. The complexes with mixed ligands favorably combine reactivity and stability. Calculations on the ligand dissociation from [CpCo(olefin)(phosphite)] proved that the phosphite is dissociating before the olefin. [CpCo(H2C?CHSiMe3){P(OPh)3}] ( 2 a ) was investigated for the co‐cyclization of diynes and nitriles and found to be an efficient catalyst at rather mild temperatures. 相似文献
3.
A series of iridium tetrahydride complexes [Ir(H)4(PSiP‐R)] bearing a tridentate pincer‐type bis(phosphino)silyl ligand ([{2‐(R2P)C6H4}2MeSi]−, PSiP‐R, R=Cy, iPr, or tBu) were synthesized by the reduction of [IrCl(H)(PSiP‐R)] with Me4N ⋅ BH4 under argon. The same reaction under a nitrogen atmosphere afforded a rare example of thermally stable iridium(III)–dinitrogen complexes, [Ir(H)2(N2)(PSiP‐R)]. Two isomeric dinitrogen complexes were produced, in which the PSiP ligand coordinated to the iridium center in meridional and facial orientations, respectively. Attempted substitution of the dinitrogen ligand in [Ir(H)2(N2)(PSiP‐Cy)] with PMe3 required heating at 150 °C to give the expected [Ir(H)2(PMe3)(PSiP‐Cy)] and a trigonal bipyramidal iridium(I)–dinitrogen complex, [Ir(N2)(PMe3)(PSiP‐Cy)]. The reaction of [Ir(H)4(PSiP‐Cy)] with three equivalents of 2‐norbornene (nbe) in benzene afforded [IrI(nbe)(PSiP‐Cy)] in a high yield, while a similar reaction of [Ir(H)4(PSiP‐R)] with an excess of 3,3‐dimethylbutene (tbe) in benzene gave the C H bond activation product, [IrIII(H)(Ph)(PSiP‐R)], in high yield. The oxidative addition of benzene is reversible; heating [IrIII(H)(Ph)(PSiP‐Cy)] in the presence of PPh3 in benzene resulted in reductive elimination of benzene, coordination of PPh3, and activation of the C H bond of one aromatic ring in PPh3. [IrIII(H)(Ph)(PSiP‐R)] catalyzed a direct borylation reaction of the benzene C H bond with bis(pinacolato)diboron. Molecular structures of most of the new complexes in this study were determined by a single‐crystal X‐ray analysis. 相似文献
4.
Pei Nian Liu Dr. Fu Hai Su Dr. Ting Bin Wen Dr. Herman H.‐Y. Sung Dr. Ian D. Williams Prof. Dr. Guochen Jia Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(26):7889-7897
The new ruthenium complex [Ru(N3P)(OAc)][BPh4] ( 4 ), in which N3P is the N,P mixed tetradentate ligand N,N‐bis[(pyridin‐2‐yl)methyl]‐[2‐(diphenylphosphino)phenyl]methanamine was synthesized. The complex was found to be catalytically active for the endo cycloisomerization of alkynols. The catalytic reactions can be used to synthesize five‐, six‐, and seven‐membered endo‐cyclic enol ethers in good to excellent yields. A catalytic cycle involving a vinylidene intermediate was proposed for the catalytic reactions. Treatment of complex 4 with PhC?CH and H2O gave the alkyl complex [Ru(CH2Ph)(CO)(N3P)][BPh4] ( 30 ), which supports the assumption that the catalytic reactions involve addition of a hydroxyl group to the C?C bond of vinylidene ligands. 相似文献
5.
Multifaceted Coordination Chemistry of Vanadium(V): Substitution, Rearrangement Reactions, and Condensation Reactions of Oxovanadium(V) Complexes of the Tripodal Oxygen Ligand LOMe? = [η5‐(C5H5)Co{P(OMe)2(O)}3]? The octahedral oxovanadium(V) complex [V(O)F2LOMe] of the tripodal oxygen ligand LOMe? = [η5‐(C5H5)Co{P(OMe)2(O)}3]? reacts with alcohols and phenol with substitution of one fluoride ligand to form alkoxo complexes [V(O)F(OR)LOMe], R = Me, Et, i‐Prop, Ph. In the presence of water, however, both fluoride ions are substituted and a complex with the composition VO2LOMe can be isolated. The crystal structure shows that the oxo‐bridged trimer [{V(O)(LOMe)O}3] was synthesized. In the presence of BF3 the fluoride ligand in the alkoxo‐complex [V(O)F(OEt)LOMe] can be exchanged for pyridine to yield [V(O)(OEt)pyLOMe]BF4. Analogous attempts to exchange the fluoride ligand for tetrahydrofuran and acetonitrile induces a rearrangement reaction that leads to the vanadium complex [V(O)(LOMe)2]BF4. The crystal structure of this compound has been determined. Its 1H and 31P‐NMR spectra show that it is a highly fluxional vanadium complex at ambient temperature in solution. The two tripodal ligands LOMe? coordinate the vanadium centre as bidentate or tridentate ligands. The exchange bidentate/tridentate becomes slow on the NMR time scale below about 200 K. 相似文献
6.
Sandra Bolaño Jorge Bravo Prof. Dr. Jesús Castro Soledad García‐Fontán Elvira Lamas Pilar Rodríguez Seoane 《无机化学与普通化学杂志》2009,635(15):2503-2510
Hydrido complexes [MnH(CO)3L1–3] [L1 = 1,2‐bis‐(diphenylphosphanoxy)‐ethane ( 1 ); L2 = 1,2‐bis‐(diisopropylphosphanoxy)ethane ( 2 ); L3 = 1,3‐bis‐(diphenylphosphanoxy)‐propane ( 3 )] were prepared by treating [MnH(CO)5] with the appropriate bidentate ligand by heating to reflux. Photoirradiation of a toluene solution of complexes 1 and 2 in the presence of PPhn(OR)3–n (n = 0, 1; R = Me, Et) leads to the replacement of a CO ligand by the corresponding monodentate phosphite or phosphonite ligand to give new hydrido compounds of formula [MnH(CO)2(L1–2)(L)] [L = P(OMe)3 ( 1a – 2a ); P(OEt)3 ( 1b – 2b ); PPh(OMe)2 ( 1c – 2c ); PPh(OEt)2 ( 1d – 2d )]. All complexes were characterized by IR, 1H, 13C and 31P NMR spectroscopy. In case of compounds 2 and 3 , suitable crystals for X‐ray diffraction studies were isolated. 相似文献
7.
The reaction of [ReBr(CO)5] with phosphite and phosphonite ligands in toluene yielded cis, mer‐[ReBr(CO)2L3] ( 2 : L = P(OMe)3 2a : P(OEt)3 2b : PPh(OMe)2 2c : PPh(OEt)2 2d ). Compounds 2c and 2d were also obtained, as were the phosphinite complexes 2e [L = PPh2(OMe)] and 2f [L = PPh2(OEt)], by reaction of the corresponding phosphorus ligand with trans, mer‐[ReBr(CO)3L2]. Compounds 2 were all characterized by elemental analysis, mass spectrometry and NMR spectroscopy, and the structures of 2b , 2c and 2d were determined by X‐ray diffractometry. Compounds 2a‐d are stable in chloroform and dichloromethane, but 2e and 2f are transformed into the corresponding trans, mer‐[ReBr(CO)3L2] complexes by a reaction for which a partial mechanism is put forward. 相似文献
8.
Adam Neuba Dr. Sonja Herres‐Pawlis Oliver Seewald Janna Börner Andreas J. Heuwing Ulrich Flörke Prof. Dr. Gerald Henkel 《无机化学与普通化学杂志》2010,636(15):2641-2649
The transition metal complexes with the ligand 1,3‐bis(N,N,N′,N′‐tetramethylguanidino)propane (btmgp), [Mn(btmgp)Br2] ( 1 ), [Co(btmgp)Cl2] ( 2 ), [Ni(btmgp)I2] ( 3 ), [Zn(btmgp)Cl2] ( 4 ), [Zn(btmgp)(O2CCH3)2] ( 5 ), [Cd(btmgp)Cl2] ( 6 ), [Hg(btmgp)Cl2] ( 7 ) and [Ag2(btmgp)2][ClO4]2·2MeCN ( 8 ), were prepared and characterised for the first time. The stoichiometric reaction of the corresponding water‐free metal salts with the ligand btmgp in dry MeCN or THF resulted in the straightforward formation of the mononuclear complexes 1 – 7 and the binuclear complex 8 . In complexes with MII the metal ion shows a distorted tetrahedral coordination whereas in 8 , the coordination of the MI ion is almost linear. The coordination behavior of btmgp and resulting structural parameters of the corresponding complexes were discussed in an comparative approach together with already described complexes of btmgp and the bisguanidine ligand N1,N2‐bis(1,3‐dimethylimidazolidin‐2‐ylidene)‐ethane‐1,2‐diamine (DMEG2e), respectively. 相似文献
9.
Cristina Tejel Dr. M. Pilar del Río Dr. Miguel A. Ciriano Prof. Dr. Eduard J. Reijerse Dr. František Hartl Prof. Stanislav Záliš Dr. Dennis G. H. Hetterscheid Dr. Nearchos Tsichlis i Spithas Bas de Bruin Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):11878-11889
Treatment of [Ir(bpa)(cod)]+ complex [ 1 ]+ with a strong base (e.g., tBuO?) led to unexpected double deprotonation to form the anionic [Ir(bpa?2H)(cod)]? species [ 3 ]?, via the mono‐deprotonated neutral amido complex [Ir(bpa?H)(cod)] as an isolable intermediate. A certain degree of aromaticity of the obtained metal–chelate ring may explain the favourable double deprotonation. The rhodium analogue [ 4 ]? was prepared in situ. The new species [M(bpa?2H)(cod)]? (M=Rh, Ir) are best described as two‐electron reduced analogues of the cationic imine complexes [MI(cod)(Py‐CH2‐N?CH‐Py)]+. One‐electron oxidation of [ 3 ]? and [ 4 ]? produced the ligand radical complexes [ 3 ]. and [ 4 ].. Oxygenation of [ 3 ]? with O2 gave the neutral carboxamido complex [Ir(cod)(py‐CH2‐N‐CO‐py)] via the ligand radical complex [ 3 ]. as a detectable intermediate. 相似文献
10.
Gustavo Santiso‐Quinones Rafael E. Rodriguez‐Lugo 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(8):859-861
The compound [2‐(aminomethyl)pyridine‐κ2N,N′][chlorido/trifluoromethanesulfonato(0.91/0.09)][(10,11‐η)‐5H‐dibenzo[a,d]cyclohepten‐5‐amine‐κN](triphenylphosphane‐κP)ruthenium(II) trifluoromethanesulfonate dichloromethane 0.91‐solvate, [Ru(CF3SO3)0.09Cl0.91(C6H8N2)(C15H13N)(C18H15P)]CF3SO3·0.91CH2Cl2, belongs to a series of RuII complexes that had been tested for transfer hydrogenation, hydrogenation of polar bonds and catalytic transfer hydrogenation. The crystal structure determination of this complex revealed disorder in the form of two different anionic ligands sharing the same coordination site, which other spectroscopic methods failed to characterize. The reduced catalytic activity of the title compound was not fully understood until the crystallographic data provided evidence for the mixed ligand species. The crystal structure clearly shows that the majority of the synthesized material has a chloride ligand present. Only a small portion of the material is the expected complex [RuII(OTf)(ampy)(η2‐tropNH2)(PPh3)]OTf, where OTf is triflate or trifluoromethanesulfonate, ampy is 2‐(aminomethyl)pyridine and tropNH2 is 5H‐dibenzo[a,d]cyclohepten‐5‐amine. 相似文献
11.
《Angewandte Chemie (International ed. in English)》2017,56(10):2720-2724
N‐Heterocyclic carbene based pincer ligands bearing a central silyl donor, [CSiC]−, have been envisioned as a class of strongly σ‐donating ligands that can be used for synthesizing electron‐rich transition‐metal complexes for the activation of inert bonds. However, this type of pincer ligand and complexes thereof have remained elusive owing to their challenging synthesis. We herein describe the first synthesis of a CSiC pincer ligand scaffold through the coupling of a silyl–NHC chelate with a benzyl–NHC chelate induced by one‐electron oxidation in the coordination sphere of a cobalt complex. The monoanionic CSiC ligand stabilizes the CoI dinitrogen complex [(CSiC)Co(N2)] with an unusual coordination geometry and enables the challenging oxidative addition of E−H bonds (E=C, N, O) to CoI to form CoIII complexes. The structure and reactivity of the cobalt(I) complex are ascribed to the unique electronic properties of the CSiC pincer ligand, which provides a strong trans effect and pronounced σ‐donation. 相似文献
12.
Kaijie Xu Mingwei Hong Yicheng Zhang Li Song Wenxiang Chai 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(9):858-861
In the title heteroleptic cuprous complex, (acetonitrile‐κN)({2‐[2‐(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane‐κ2P,P′)[2‐(pyridin‐4‐yl‐κN)‐1,3‐benzoxazole]copper(I) hexafluoridophosphate, [Cu(C36H28OP2)(CH3CN)(C12H8N2O)]PF6, conventionally abbreviated [Cu(POP)(CH3CN)(4‐PBO)]PF6, where POP is the diphosphane ligand {2‐[2‐(diphenylphosphanyl)phenoxy]phenyl}diphenylphosphane and 4‐PBO is the N‐containing ligand 2‐(pyridin‐4‐yl)‐1,3‐benzoxazole, the asymmetric unit consists of a hexafluoridophosphate anion and a whole mononuclear cation, where the CuI centre is coordinated by two P atoms from the POP ligand, by one N atom from the 4‐PBO ligand and by the N atom of the coordinated acetonitrile molecule, giving rise to a CuP2N2 distorted tetrahedral coordination geometry. The electronic absorption, photoluminescence and thermal stability properties of this complex have been studied on as‐synthesized samples, which had previously been examined by powder X‐ray diffraction. A yellow emission signal is attributed to an excited state arising from metal‐to‐ligand charge transfer (MLCT). 相似文献
13.
Steric Effects on the Structures,Reactivity, and Coordination Chemistry of Tris(2‐pyridyl)aluminates
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Dr. Raúl García‐Rodríguez Prof. Dominic S. Wright 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14949-14957
Introducing substituents in the 6‐position of the 2‐pyridyl rings of tris(pyridyl)aluminate anions, of the type [EtAl(2‐py′)3]? (py′=a substituted 2‐pyridyl group), has a large impact on their metal coordination characteristics. This is seen most remarkably in the desolvation of the THF solvate [EtAl(6‐Me‐2‐py)3Li?THF] to give the monomer [EtAl(6‐Me‐2‐py)3Li] ( 1 ), containing a pyramidal, three‐coordinate Li+ cation. Similar monomeric complexes are observed for [EtAl(6‐CF3‐2‐py)3Li] ( 2 ) and [EtAl(6‐Br‐2‐py)3Li] ( 3 ), which contain CF3 and Br substituents (R). This steric influence can be exploited in the synthesis of a new class of terminal Al?OH complexes, as is seen in the controlled hydrolysis of 2 and 3 to give [EtAl(OH)(6‐R‐2‐py)2]? anions, as in the dimer [EtAl(OH)(6‐Br‐2‐py)2Li]2 ( 5 ). Attempts to deprotonate the Al?OH group of 5 using Et2Zn led only to the formation of the zincate complex [LiZn(6‐Br‐py)3]2 ( 6 ), while reactions of the 6‐Br substituted 3 and the unsubstituted complex [EtAl(2‐py)3Li] with MeOH give [EtAl(OMe)(6‐Br‐2‐py)2Li]2 ( 7 ) and [EtAl(OMe)(2‐py)2Li]2 ( 8 ), respectively, having similar dimeric arrangements to 5 . The combined studies presented provide key synthetic methods for the functionalization and elaboration of tris(pyridyl)aluminate ligands. 相似文献
14.
β‐Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands
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Dr. Luis M. Martínez‐Prieto Elena Ávila Dr. Pilar Palma Dr. Eleuterio Álvarez Prof. Dr. Juan Cámpora 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9833-9849
Nickel and palladium methoxides [(iPrPCP)M‐OMe], which contain the iPrPCP pincer ligand, decompose upon heating to give products of different kinds. The palladium derivative cleanly gives the dimeric Pd0 complex [Pd(μ‐iPrPCHP)]2 (iPrPCHP=2,6‐bis(diisopropylphosphinomethyl)phenyl) and formaldehyde. In contrast, decomposition of [(iPrPCP)Ni‐OMe] affords polynuclear carbonyl phosphine complexes. Both decomposition processes are initiated by β‐hydrogen elimination (BHE), but the resulting [(iPrPCP)M‐H] hydrides undergo divergent reaction sequences that ultimately lead to the irreversible breakdown of the pincer units. Whereas the Pd hydride spontaneously experiences reductive C?H coupling, the decay of its Ni analogue is brought about by its reaction with formaldehyde released in the BHE step. Kinetic measurements showed that the BHE reaction is reversible and less favourable for Ni than for Pd for both kinetic and thermodynamic reasons. DFT calculations confirmed the main conclusions of the kinetic studies and provided further insight into the mechanisms of the decomposition reactions. 相似文献
15.
Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl‐alkylamine Ligands on Spin Crossover Properties
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Michael Leibold Sandra Kisslinger Frank W. Heinemann Frank Hampel Yuko Ichiyanagi Michael Klein Patrick Homenya Franz Renz Siegfried Schneider Markus Reiher Siegfried Schindler 《无机化学与普通化学杂志》2016,642(1):85-94
Iron(II) complexes of the type [Fe(L)(NCS)2] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)2] [tmpa = tris(2‐pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)2], [Fe(pmap)(NCS)2], and [Fe(tepa)(NCS)2] [pmea = N,N‐bis[(2‐pyridyl)methyl]‐2‐(2‐pyridyl)ethylamine, pmap = N,N‐bis[2‐(2‐pyridyl)ethyl]‐(2‐pyridyl)methylamine, and tepa = tris[2‐(2‐pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Mößbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl‐alkylamine ligands is clearly demonstrated. 相似文献
16.
Isolde Bachert Irene Bartusseck Pierre Braunstein Emmanuel Guillon Jacky Ros Guido Kickelbick 《Journal of organometallic chemistry》1999,580(2):3016
Heterometallic triangular platinum–cobalt, palladium–cobalt and palladium–molybdenum clusters stabilized by one or two bridging diphosphine ligands such as Ph2PNHPPh2 (dppa) or (Ph2P)2NMe (dppaMe) or by mixed ligand sets Ph2PCH2PPh2 (dppm)/dppa have been prepared with the objectives of comparing the stability and properties of the clusters as a function of the short-bite diphosphine ligand used and of the metal carbonyl fragment they contain. Ligand redistribution reactions were observed during the purification of [Co2Pd(μ3-CO)(CO)4(μ-dppa)(μ-dppm)] (4) by column chromatography with the formation of [Co2Pd(μ3-CO)(CO)4(μ-dppm)2] and the dinuclear complex [(OC)2
Cl] (5). The latter was independently prepared by reaction of [Pd(dppa-P,P′)2](BF4)2 with Na[Co(CO)4]. Attempts to directly incorporate the ligand (Ph2P)2N(CH2)3Si(OMe)3 (dppaSi) into a cluster or to generate it by N-functionalization of coordinated dppa were unsuccessful, in contrast to results obtained recently with related clusters. The crystal structure of [Co2Pt(μ3-CO)(CO)6(μ-dppa)] (1) has been determined by X-ray diffraction. 相似文献
17.
Orde Q. Munro Greville L. Camp 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(4):m132-m135
(Diphenyl phosphite‐κO)(5,10,15,20‐tetraphenylporphyrinato‐κ4N)manganese(III) hexafluoroantimonate(V), [Mn(C44H28N4)(C12H11O3P)](SbF6), is the first example of a structurally characterized diaryl or dialkyl phosphite complex of a metal–porphyrin ion. The axial phosphite ligand binds to the MnIII ion via the P=O O atom, affording a nominally five‐coordinate complex with an Mn—O distance of 2.120 (4) Å. The mean porphyrin Mn—N distance is 2.000 (4) Å and the MnIII ion is displaced from the 24‐atom porphyrin mean plane by 0.1548 (13) Å towards the axial O atom. The porphyrin adopts a marked saddle conformation, with a small domed component. The saddle distortion of the porphyrin ligand reflects the tight back‐to‐back dimers formed in the lattice by pairs of neighboring cations. The `non‐covalent' dimers in the lattice exhibit an unusual (weak) η2‐type coordination of a pyrrole C=C bond from a neighboring molecule, with MnIII⃛C distances of 3.697 (5) and 3.537 (5) Å. 相似文献
18.
Howard M. Colquhoun Ann M. Chippindale Yun Fu Chan 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(12):m390-m393
Nucleophilic attack of (triphenylphosphonio)cyclopentadienide on the dichlorodiazomethane–tungsten complex trans‐[BrW(dppe)2(N2CCl2)]PF6 [dppe is 1,2‐bis(diphenylphosphino)ethane] results in C—C bond formation and affords the title compound, trans‐[W(C24H18ClN2P)Br(C26H24P2)2]PF6·0.6CH2Cl2. This complex, bis[1,2‐bis(diphenylphosphino)ethane]bromido{chloro[3‐(triphenylphosphonio)cyclopentadienylidene]diazomethanediido}tungsten hexafluorophosphate dichloromethane 0.6‐solvate, contains the previously unknown ligand chloro[3‐(triphenylphosphonio)cyclopentadienylidene]diazomethane. Evidence from bond lengths and torsion angles indicates significant through‐ligand delocalization of electron density from tungsten to the nominally cationic phosphorus(V) centre. This structural analysis clearly demonstrates that the tungsten–dinitrogen unit is a powerful π‐electron donor with the ability to transfer electron density from the metal to a distant acceptor centre through an extended conjugated ligand system. As a consequence, complexes of this type could have potential applications as nonlinear optical materials and molecular semiconductors. 相似文献
19.
Sahebeh Nikahd Reza Babadi Aghakhanpour S. Masoud Nabavizadeh Fatemeh Niroomand Hosseini S. Jafar Hoseini Arno Pfitzner Mozhgan Samandar Sangari 《应用有机金属化学》2019,33(11)
A new series of cycloplatinated (II) complexes with general formulas of [Pt (bhq)(N3)(P)] [bhq = deprotonated 7,8‐benzo[h]quinoline, P = triphenyl phosphine (PPh3) and methyldiphenyl phosphine], [Pt (bhq)(P^P)]N3 [P^P = 1,1‐bis (diphenylphosphino)methane (dppm) and 1,2‐bis (diphenylphosphino)ethane] and [Pt2(bhq)2(μ‐P^P)(N3)2] [P^P = dppm and 1,2‐bis (diphenylphosphino)acetylene] is reported in this investigation. A combination of azide (N3?) and phosphine (monodentate and bidentate) was used as ancillary ligands to study their influences on the chromophoric cyclometalated ligand. All complexes were characterized by nuclear magnetic resonance spectroscopy. To confirm the presence of the N3? ligand directly connected to the platinum center, complex [Pt (bhq)(N3)(PPh3)] was further characterized by single‐crystal X‐ray crystallography. The photophysical properties of the new products were studied by UV–Vis spectroscopy in CH2Cl2 and photoluminescence spectroscopy in solid state (298 or 77 K) and in solution (77 K). Using density functional theory calculations, it was proved that, in addition to intraligand charge‐transfer (ILCT) and metal‐to‐ligand charge‐transfer (MLCT) transitions, the L′LCT (L′ = N3, L = C^N) electronic transition has a remarkable contribution in low energy bands of the absorption spectra (for complexes [Pt (bhq)(N3)(P)] and [Pt2(bhq)2(μ‐P^P)(N3)2]). It is indicative of the determining role of the N3? ligand in electronic transitions of these complexes, specifically in the low energy region. In this regard, the photoluminescence studies indicated that the emissions in such complexes originate from a mixed 3ILCT/3MLCT (intramolecular) and also from aggregations (intermolecular). 相似文献
20.
Srinivas Anga Mitali Paul Kishor Naktode Ravi K. Kottalanka Prof. Dr. Tarun K. Panda 《无机化学与普通化学杂志》2012,638(9):1311-1315
The cobalt(II) complex [CoCl2(2, 6‐iPrC6H3‐BIAO)]2 ( 1 ) of rigid unsymmetrical imine, carbonyl mixed ligand [N‐(2, 6‐diisopropylphenyl)‐imino]acenapthenone] (2, 6‐iPrC6H3‐BIAO) ( L1 ) can be achieved by the reaction of CoCl2 and neutral [N‐(2, 6‐diisopropylphenyl)‐imino]acenapthenone] ligand. When ligand L1 reacted with CuCl in dichloromethane solution, only nitrogen coordinated copper complex [CuCl(2, 6‐iPrC6H3‐BIAO)] ( 2 ) was obtained. In the solid‐state structure, compound 1 is dimeric through the chelating two μ2 chlorine atoms and each cobalt atom adopts either a distorted trigonal bipyramidal or a distorted square pyramidal arrangement. In contrast, the molecular structure of compound 2 reveals that copper is coordinated by imino nitrogen and adopts a linear arrangement around the central metal atom. The crystal structure of the rigid bidentate mixed nitrogen and oxygen ligand (2, 6‐iPrC6H3‐BIAO) ( L1 ) is also reported. 相似文献