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1.
Chi‐Kin Koo Dr. Ka‐Leung Wong Dr. Kai‐Cheung Lau Prof. Wai‐Yeung Wong Prof. Michael Hon‐Wah Lam Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(31):7689-7697
The bis(diphenylphosphino)methane (dppm)‐bridged dinuclear cycloplatinated complex {[Pt(L)]2(μ‐dppm)}2+ (Pt2 ? dppm; HL: 2‐phenyl‐6‐(1H‐pyrazol‐3‐yl)‐pyridine) demonstrates interesting reversible “pivot‐hinge”‐like intramolecular motions in response to the protonation/deprotonation of L. In its protonated “closed” configuration, the two platinum(II) centers are held in position by intramolecular d8–d8 Pt–Pt interaction. In its deprotonated “open” configuration, such Pt–Pt interaction is cleaved. To further understand the mechanism behind this hingelike motion, an analogous dinuclear cycloplatinated complex, {[Pt(L)]2(μ‐dchpm)}2+ (Pt2 ? dchpm) with bis(dicyclohexylphosphino)methane (dchpm) as the bridging ligand, was synthesized. From its protonation/deprotonation responses, it was revealed that aromatic π–π interactions between the phenyl moieties of the μ‐dppm and the deprotonated pyrazolyl rings of L was essential to the reversible cleavage of the intramolecular Pt–Pt interaction in Pt2 ? dppm. In the case of Pt2 ? dchpm, spectroscopic and spectrofluorometric titrations as well as X‐ray crystallography indicated that the distance between the two platinum(II) centers shrank upon deprotonation, thus causing a redshift in its room‐temperature triplet metal–metal‐to‐ligand charge‐transfer emission from 614 to 625 nm. Ab initio calculations revealed the presence of intramolecular hydrogen bonding between the deprotonated and negatively charged 1‐pyrazolyl‐N moiety and the methylene CH and phenyl C–H of the μ‐dppm. The “open” configuration of the deprotonated Pt2 ? dppm was estimated to be 19 kcal mol?1 more stable than its alternative “closed” configuration. On the other hand, the open configuration of the deprotonated Pt2 ? dchpm was 6 kcal mol?1 less stable than its alternative closed configuration. 相似文献
2.
Yoshiki Ozawa Misa Kim Koshiro Toriumi 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(2):146-149
A new one‐dimensional platinum mixed‐valence complex with nonhalogen bridging ligands, namely catena‐poly[[[bis(ethane‐1,2‐diamine‐κ2N,N′)platinum(II)]‐μ‐thiocyanato‐κ2S:S‐[bis(ethane‐1,2‐diamine‐κ2N,N′)platinum(IV)]‐μ‐thiocyanato‐κ2S:S] tetrakis(perchlorate)], {[Pt2(SCN)2(C2H8N2)4](ClO4)4}n, has been isolated. The PtII and PtIV atoms are located on centres of inversion and are stacked alternately, linked by the S atoms of the thiocyanate ligands, forming an infinite one‐dimensional chain. The PtIV—S and PtII...S distances are 2.3933 (10) and 3.4705 (10) Å, respectively, and the PtIV—S...PtII angle is 171.97 (4)°. The introduction of nonhalogen atoms as bridging ligands in this complex extends the chemical modifications possible for controlling the amplitude of the charge‐density wave (CDW) state in one‐dimensional mixed‐valence complexes. The structure of a discrete PtIV thiocyanate compound, bis(ethane‐1,2‐diamine‐κ2N,N′)bis(thiocyanato‐κS)platinum(IV) bis(perchlorate) 1.5‐hydrate, [Pt(SCN)2(C4H8N2)2](ClO4)2·1.5H2O, has monoclinic (C2) symmetry. Two S‐bound thiocyanate ligands are located in trans positions, with an S—Pt—S angle of 177.56 (3)°. 相似文献
3.
Nobuyuki Matsushita Ayako Taira 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(12):1033-1036
The title compound, catena‐poly[[[bis(ethylenediamine‐κ2N,N′)platinum(II)]‐ μ‐chlorido‐[bis(ethylenediamine)platinum(IV)]‐μ‐chlorido] tetrakis{4‐[(4‐hydroxyphenyl)diazenyl]benzenesulfonate} dihydrate], {[PtIIPtIVCl2(C2H8N2)4](HOC6H4N=NC6H4SO3)4·2H2O}n, has a linear chain structure composed of square‐planar [Pt(en)2]2+ (en is ethylenediamine) and elongated octahedral trans‐[PtCl2(en)2]2+ cations stacked alternately, bridged by Cl atoms, along the b axis. The Pt atoms are located on an inversion centre, while the Cl atoms are disordered over two sites and form a zigzag ...Cl—PtIV—Cl...PtII... chain, with a PtIV—Cl bond length of 2.3140 (14) Å, an interatomic PtII...Cl distance of 3.5969 (15) Å and a PtIV—Cl...PtII angle of 170.66 (6)°. The structural parameter indicating the mixed‐valence state of the Pt atom, expressed by δ = (PtIV—Cl)/(PtII...Cl), is 0.643. 相似文献
4.
Platinum‐Containing Polyoxometalates: syn‐ and anti‐[PtII2(α‐PW11O39)2]10− and Formation of the Metal–Metal‐Bonded di‐PtIII Derivatives
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Dr. Zhengguo Lin Dr. Natalya V. Izarova Aleksandar Kondinski Xiaolin Xing Dr. Ali Haider Linyuan Fan Dr. Nina Vankova Prof. Thomas Heine Dr. Bineta Keita Prof. Jie Cao Prof. Changwen Hu Prof. Ulrich Kortz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5514-5519
The first examples of dimeric, di‐PtII‐containing heteropolytungstates are reported. The two isomeric di‐platinum(II)‐containing 22‐tungsto‐2‐phosphates [anti‐PtII2(α‐PW11O39)2]10? ( 1 a ) and [syn‐PtII2(α‐PW11O39)2]10? ( 2 a ) were synthesized in aqueous pH 3.5 medium using one‐pot procedures. Polyanions 1 a and 2 a contain a core comprising two face‐on PtO4 units, with a Pt???Pt distance of 2.9–3 Å. Both polyanions were investigated by single‐crystal XRD, IR, TGA, UV/Vis, 31P NMR, ESI‐MS, CID‐MS/MS, electrochemistry, and DFT. On the basis of DFT and electrochemistry, we demonstrated that the {Pt2II} moiety in 1 a and 2 a can undergo fully reversible two‐electron oxidation to {Pt2III}, accompanied by formation of a single Pt?Pt bond. Hence we have discovered the novel subclass of PtIII‐containing heteropolytungstates. 相似文献
5.
Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems
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Brandon R. Barnett Prof. Arnold L. Rheingold Prof. Joshua S. Figueroa 《Angewandte Chemie (International ed. in English)》2016,55(32):9253-9258
Owing to their unique topologies and abilities to self‐assemble into a variety of extended and aggregated structures, the binary platinum carbonyl clusters [Pt3(CO)6]n2? (“Chini clusters”) continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron‐transfer series [Pt3(μ‐CO)3(CNArDipp2)3]n? (n=0, 1, 2), which represents a unique set of monomeric Pt3 clusters supported by π‐acidic ligands. Spectroscopic, computational, and synthetic investigations demonstrate that the highest‐occupied molecular orbitals of the mono‐ and dianionic clusters consist of a combined π*‐framework of the CO and CNArDipp2 ligands, with negligible Pt character. Accordingly, this study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in a redox non‐innocent manner. 相似文献
6.
Planar 2‐Pyridyl‐1,2,3‐triazole Derived Metallo‐ligands: Self‐assembly with PdCl2 and Photocatalysis
Natalie R. Lagesse Kelvin Y. L. Tan James D. Crowley James A. Findlay 《化学:亚洲杂志》2020,15(10):1567-1573
Self‐assembled metallosupramolecular architectures (MSAs) with built‐in functionalities such as light‐harvesting metal centers are a promising approach for developing emergent properties within discrete molecular systems. Herein we describe the synthesis of two new but simple “click” ligands featuring a bidentate 2‐pyridyl‐1,2,3‐triazole chelate pocket linked to a monodentate pyridyl (either 3‐ or 4‐substituted, L1 and L2 ) unit. The ligands and the corresponding four PdIIand PtIImetallo‐ligands ( Pd1 , Pd2 , Pt1 and Pt2 ) were synthesized and characterized using nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and X‐ray crystallography. Solid‐state characterization of the series of ligands and metallo‐ligands revealed that these compounds display a co‐planar conformation of all the aryl units. The PtIIcontaining metallo‐ligands ( Pt1 and Pt2 ) were found to assemble into square ( Sqr ) and triangular ( Tri ) shaped architectures when combined with neutral PdCl2 linker units. Additionally, the ability of the PtIImetallo‐ligands and Tri to photocatalyze the cycloaddition of singlet oxygen to anthracene was investigated. 相似文献
7.
Zhong‐Ming Sun Dr. Shuo‐Ping Chen Pinjing Zhao Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(8):2619-2627
A convenient and waste‐free synthesis of indene‐based tertiary carbinamines by rhodium‐catalyzed imine/alkyne [3+2] annulation is described. Under the optimized conditions of 0.5–2.5 mol % [{(cod)Rh(OH)}2] (cod=1,5‐cyclooctadiene) catalyst, 1,3‐bis(diphenylphosphanyl)propane (DPPP) ligand, in toluene at 120 °C, N‐unsubstituted aromatic ketimines and internal alkynes were coupled in a 1:1 ratio to form tertiary 1H‐inden‐1‐amines in good yields and with high selectivities over isoquinoline products. A plausible catalytic cycle involves sequential imine‐directed aromatic C? H bond activation, alkyne insertion, and a rare example of intramolecular ketimine insertion into a RhI–alkenyl linkage. 相似文献
8.
Philipp von Grebe Dr. Pablo J. Sanz Miguel Prof. Dr. Bernhard Lippert 《无机化学与普通化学杂志》2012,638(11):1691-1698
Acid‐base and ligating properties of three bis(substituted)pyrazine (pz) and pyrimidine (pym) ligands (pyrazine‐2, 5‐dicarboxylic acid, 2, 5‐pzdcH2, 2, 3‐bis(pyridine‐2‐yl)pyrazine, 2, 3‐bppz, pyrimidine‐4, 6‐dicarboxylic acid, 4, 6‐pmdcH2) toward cis‐PtIIa2 (a = NH3, a2 = en, a2 = 2, 2′‐bpy) have been studied. Combinations of pz‐N/pym‐N with donor atoms of the substituents lead to 5‐membered platinum chelates, but exclusive N, N‐coordination through the pyridyl substituents of 2, 3‐bppz can lead to a 7‐membered platinum chelate with a characteristic L‐shape of the resulting cation. It is observed for PtII(2, 2′‐bpy), yet not for PtII(en), and is a consequence of differences in sterical interactions between the 2, 3‐bppz ligand and the coligands of PtII. 相似文献
9.
Tarlok S. Lobana Prof. Parminderjit Kaur Geeta Hundal Ray J. Butcher Alfonso Castineiras 《无机化学与普通化学杂志》2008,634(4):747-753
Reactions of pyrimidine‐2‐thione (HpymS) with PdII/PtIV salts in the presence of triphenyl phosphine and bis(diphenylphosphino)alkanes, Ph2P‐(CH2)m‐PPh2 (m = 1, 2) have yielded two types of complexes, viz. a) [M(η2‐N, S‐ pymS)(η1‐S‐ pymS)(PPh3)] (M = Pd, 1 ; Pt, 2 ), and (b) [M(η1‐S‐pymS)2(L‐L)] {L‐L, M = dppm (m = 1) Pd, 3 ; Pt, 4 ; dppe (m = 2), Pd, 5 ; Pt, 6 }. Complexes have been characterized by elemental analysis (C, H, N), NMR spectroscopy (1H, 13C, 31P), and single crystal X‐ray crystallography ( 1 , 2 , 4 , and 5 ). Complexes 1 and 2 have terminal η1‐S and chelating η2‐N, S‐modes of pymS−, while other Pd/Pt complexes have only terminal η1‐S modes. The solution state 31P NMR spectral data reveal dynamic equilibrium for the complexes 3 , 5 and 6 , whereas the complexes 1 , 2 and 4 are static in solution state. 相似文献
10.
Jing Liu Menggai Jiao Bingbao Mei Yuxin Tong Yuping Li Mingbo Ruan Ping Song Gongquan Sun Luhua Jiang Ying Wang Zheng Jiang Lin Gu Zhen Zhou Weilin Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(4):1175-1179
Maximizing the platinum utilization in electrocatalysts toward oxygen reduction reaction (ORR) is very desirable for large‐scale sustainable application of Pt in energy systems. A cost‐effective carbon‐supported carbon‐defect‐anchored platinum single‐atom electrocatalysts (Pt1/C) with remarkable ORR performance is reported. An acidic H2/O2 single cell with Pt1/C as cathode delivers a maximum power density of 520 mW cm?2 at 80 °C, corresponding to a superhigh platinum utilization of 0.09 gPt kW?1. Further physical characterization and density functional theory computations reveal that single Pt atoms anchored stably by four carbon atoms in carbon divacancies (Pt‐C4) are the main active centers for the observed high ORR performance. 相似文献
11.
Xue Li Jian‐Min Dou Ying Liu Lan‐Ying Zhu Pei‐Ju Zheng 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(10):1185-1187
The novel PtII–dibenzo‐18‐crown‐6 (DB18C6) title complex, μ‐[tetrakis(thiocyanato‐S)platinum(II)]‐N:N′‐bis{[2,5,8,15,18,21‐hexaoxatricyclo[20.4.0.19,14]hexacosa‐1(22),9(14),10,12,23,25‐hexaene‐κ6O]potassium(I)}, [K(C20H24O6)]2[Pt(SCN)4], has been isolated and characterized by X‐ray diffraction analysis. The structure analysis shows that the complex displays a quasi‐one‐dimensional infinite chain of two [K(DB18C6)]+ complex cations and a [Pt(SCN)4]2? anion, bridged by K+?π interactions between adjacent [K(DB18C6)]+ units. 相似文献
12.
Unprecedented 1D Mixed-metal Polynuclear Cyclometalated Platinum Complexes: Synthesis, Structural Characterization and Spectroscopic Properties 总被引:1,自引:0,他引:1
The complexes [Pt2L2(μ-dppm)](ClO4)2 (1) and {[Pt2L2(μ-dppm)Li(CH3CN)2](ClO4)3}n (2), where HL is 6-[4-(diethoxyphosphorylmethyl)phenyl]-2,2′-bipyridinyl and dppm is bis(diphenylphosphino)methane, have been synthesized and characterized. In complex 1 the platinum(Ⅱ) center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a "stairstep" configuration with one-dimensional Pt(Ⅱ)N^N^CPO- Li(Ⅰ)-OPC^N^ NPt(Ⅱ) mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325(2) and 3.1432(9) A, respectively, and display strong metal-metal-to-ligand charge-transfer (MMLCT) triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes. 相似文献
13.
Analogues of Cis‐ and Transplatin with a Rich Solution Chemistry: cis‐[PtCl2(NH3)(1‐MeC‐N3)] and trans‐[PtI2(NH3)(1‐MeC‐N3)]
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Dr. Sabine Siebel Claudia Dammann Dr. Pablo J. Sanz Miguel Prof. Dr. Thomas Drewello Dr. Gunnar Kampf Natascha Teubner Prof. Dr. Patrick J. Bednarski Priv.‐Doz. Dr. Eva Freisinger Prof. Dr. Bernhard Lippert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17827-17843
Mono(nucleobase) complexes of the general composition cis‐[PtCl2(NH3)L] with L=1‐methylcytosine, 1‐MeC ( 1 a ) and L=1‐ethyl‐5‐methylcytosine, as well as trans‐[PtX2(NH3)(1‐MeC)] with X=I ( 5 a ) and X=Br ( 5 b ) have been isolated and were characterized by X‐ray crystallography. The Pt coordination occurs through the N3 atom of the cytosine in all cases. The diaqua complexes of compounds 1 a and 5 a , cis‐[Pt(H2O)2(NH3)(1‐MeC)]2+ and trans‐[Pt(H2O)2(NH3)(1‐MeC)]2+, display a rich chemistry in aqueous solution, which is dominated by extensive condensation reactions leading to μ‐OH‐ and μ‐(1‐MeC?‐N3,N4)‐bridged species and ready oxidation of Pt to mixed‐valence state complexes as well as diplatinum(III) compounds, one of which was characterized by X‐ray crystallography: h,t‐[{Pt(NH3)2(OH)(1‐MeC?‐N3,N4)}2](NO3)2 ? 2 [NH4](NO3) ? 2 H2O. A combination of 1H NMR spectroscopy and ESI mass spectrometry was applied to identify some of the various species present in solution and the gas phase, respectively. As it turned out, mass spectrometry did not permit an unambiguous assignment of the structures of +1 cations due to the possibilities of realizing multiple bridging patterns in isomeric species, the occurrence of different tautomers, and uncertainties regarding the Pt oxidation states. Additionally, compound 1 a was found to have selective and moderate antiproliferative activity for a human cervix cancer line (SISO) compared to six other human cancer cell lines. 相似文献
14.
Dr. Thomas Weisheit Dr. Antje Kriltz Dr. Helmar Görls Prof. Dr. Grzegorz Mlostoń Prof. Dr. Wolfgang Imhof Prof. Dr. Wolfgang Weigand 《化学:亚洲杂志》2012,7(6):1383-1393
Two unsymmetrical 1,2,4‐trithiolanes ( 1d and 1e ) were reacted with [Pt0(PPh3)2(η2‐nbe)] ( 6 ; nbe=norborn‐2‐ene) and [Pt0(dppn)(η2‐nbe)] ( 11 ; dppn=1,8‐bis(diphenylphosphanyl)naphthalene)), respectively. Their treatment with compound 6 resulted in the formation of six‐membered platinacycles of type 7 , which selectively underwent fragmentation into dithiolato complexes and thiobenzophenone ( 4b ). The isolation of the first stable C‐substituted member of this class of compounds (i.e., compound 7e ) permitted kinetic studies of this process by using UV/Vis spectroscopy. These results, together with DFT calculations, allowed us to propose a mechanism for the reactions of compound 6 with 1,2,4‐trithiolanes. In contrast, similar treatment of compound 11 with compounds 1d and 1e at room temperature did not result in any reaction. Heating the appropriate samples to 110 °C led to the formation of dithiolato complexes and η2‐thioketone compounds, thus pointing to a thermally induced [3+2]‐cycloreversion of the heterocycles as an initial step of the reaction. 相似文献
15.
Dr. Sudipta Roy Christian J. Schürmann Totan Mondal Dr. Debasis Koley Dr. Regine Herbst‐Irmer Prof. Dr. Dietmar Stalke Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12629-12633
Platinum dichalcogenides have been known to exhibit two‐dimensional layered structures. Herein, we describe the syntheses, isolation, and characterization of air‐stable crystalline cyclic alkyl(amino) carbene (cAAC)‐supported monomeric platinum disulfide three‐membered ring complex [(cAAC)2Pt(S2)] ( 2 ). The highly reactive platinum(0) [(cAAC)2Pt] complex ( 1 ) with two‐coordinate platinum activates elemental sulfur to give 2 . The brown crystals of bis‐carbene platinum(II)monosulfate [(cAAC)2Pt(SO4)x(S2)1?x] ( 4 ) have been isolated when the reaction was performed in air. The dioxygen analogue of 2 was formed upon exposing the THF solution of 1 to aerial oxygen (O2). The binding of oxygen at the Pt0 center was found to be reversible. Additionally, DFT study has been performed to elucidate the electronic structure and bonding scenario of 2 , 3 , and 4 . Quantum chemical calculations showed donor–acceptor‐type interaction for the Pt?S bonds in 2 and Pt?O bonds in 3 and 4 . 相似文献
16.
Nobuyuki Matsushita 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(2):m33-m36
The title compound, {[PtIIPtIVI2(C2H8N2)4](HPO4)(H2PO4)I·3H2O}n, has a chain structure composed of square‐planar [Pt(en)2]2+ and elongated octahedral trans‐[PtI2(en)2]2+ cations (en is ethylenediamine) stacked alternately along the c axis and bridged by the I atoms; a three‐dimensionally valence‐ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetramer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O⋯O = 2.522 (10), 2.567 (10) and 2.569 (11) Å]. The Pt and I atoms form a zigzag ⋯I—PtIV—I⋯PtII⋯ chain, with PtIV—I bond distances of 2.6997 (7) and 2.6921 (7) Å, interatomic PtII⋯I distances of 3.3239 (8) and 3.2902 (7) Å, and PtIV—I⋯PtII angles of 154.52 (3) and 163.64 (3)°. The structural parameters indicating the mixed‐valence state of platinum, expressed by δ = (PtIV—I)/(PtII—I), are 0.812 and 0.818 for the two independent I atoms. 相似文献
17.
Kazuo Yokokawa Yoshimi Yokoyama Ken Sakai 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(2):m36-m41
The syntheses and crystal structures of the title Pt2II and Pt2III dimers doubly bridged with N,N‐dimethylguanidinate ligands, namely bis(μ‐N,N‐dimethylguanidinato)bis[(2,2′‐bipyridine)platinum(II)](Pt—Pt) bis(hexafluorophosphate) acetonitrile disolvate, [Pt2II(C3H8N3)2(C10H8N2)2](PF6)2·2CH3CN, (I), and guanidinium bis(μ‐N,N‐dimethylguanidinato)bis[(2,2′‐bipyridine)sulfatoplatinum(III)](Pt—Pt) bis(hexafluorophosphate) nitrate hexahydrate, (C3H10N3)[PtIII2(C3H8N3)2(SO4)2(C10H8N2)2]NO3·6H2O, (II), are reported. The oxidation of the Pt2II dimer into the Pt2III dimer results in a marked shortening of the Pt—Pt distance from 2.8512 (6) to 2.5656 (4) Å. The change is mainly compensated for by the change in the dihedral angle between the two Pt coordination planes upon oxidation, from 21.9 (2) to 16.9 (3)°. We attribute the relatively strong one‐dimensional stack of dimers achieved in the Pt2II compound in part to the strong PtII⋯C(bpy) associations (bpy is 2,2′‐bipyridine) in the crystal structure [Pt⋯C = 3.416 (10) and 3.361 (12) Å]. 相似文献
18.
Chi Nguyen Thi Thanh Thong Pham Van Hai Le Thi Hong Luc Van Meervelt 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(10):758-764
Crystallization experiments with the dinuclear chelate ring complex di‐μ‐chlorido‐bis[(η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)platinum(II)], [Pt2(C15H19O4)2Cl2], containing a derivative of the natural compound eugenol as ligand, have been performed. Using five different sets of crystallization conditions resulted in four different complexes which can be further used as starting compounds for the synthesis of Pt complexes with promising anticancer activities. In the case of vapour diffusion with the binary chloroform–diethyl ether or methylene chloride–diethyl ether systems, no change of the molecular structure was observed. Using evaporation from acetonitrile (at room temperature), dimethylformamide (DMF, at 313 K) or dimethyl sulfoxide (DMSO, at 313 K), however, resulted in the displacement of a chloride ligand by the solvent, giving, respectively, the mononuclear complexes (acetonitrile‐κN)(η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)chloridoplatinum(II) monohydrate, [Pt(C15H19O4)Cl(CH3CN)]·H2O, (η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)chlorido(dimethylformamide‐κO)platinum(II), [Pt(C15H19O4)Cl(C2H7NO)], and (η2‐2‐allyl‐4‐methoxy‐5‐{[(propan‐2‐yloxy)carbonyl]methoxy}phenyl‐κC1)chlorido(dimethyl sulfoxide‐κS)platinum(II), determined as the analogue {η2‐2‐allyl‐4‐methoxy‐5‐[(ethoxycarbonyl)methoxy]phenyl‐κC1}chlorido(dimethyl sulfoxide‐κS)platinum(II), [Pt(C14H17O4)Cl(C2H6OS)]. The crystal structures confirm that acetonitrile interacts with the PtII atom via its N atom, while for DMSO, the S atom is the coordinating atom. For the replacement, the longest of the two Pt—Cl bonds is cleaved, leading to a cis position of the solvent ligand with respect to the allyl group. The crystal packing of the complexes is characterized by dimer formation via C—H…O and C—H…π interactions, but no π–π interactions are observed despite the presence of the aromatic ring. 相似文献
19.
Atilla Karaar Matthias Freytag Peter G. Jones Rainer Bartsch Reinhard Schmutzler 《无机化学与普通化学杂志》2001,627(7):1571-1581
1,8‐Bis[(diethylamino)phosphino]naphthalene ( 1 ) reacted with dry methanol in dichloromethane to form the new bis‐phosphonite ligand 1,8‐bis[(dimethoxy)phosphino]naphthalene (dmeopn, 2 ). By oxidation of 2 with H2O2 · (H2N)2C(:O) the corresponding bis‐phosphonate, 1,8‐bis[(dimethoxy)phosphoryl]naphthalene ( 3 ), was obtained quantitatively. Reaction of 3 with phosphorus trichloride unexpectedly furnished a 2.4 : 1 mixture of the bis‐phosphonate anhydrides rac‐ and meso‐1,3‐dimethoxy‐1,3‐dioxo‐2,3‐dihydro‐1,3‐diphospha‐2‐oxaphenalene (rac‐ 4 and meso‐ 4 ) from which rac‐ 4 could be fractionally crystallised. The bis‐phosphonite 2 behaved as a normal bidentate chelate ligand towards Mo0 and PdII, and furnished the complexes [(dmeopn)Mo(CO)4] ( 5 ) and [(dmeopn)PdCl2] ( 6 ) when treated with [(nor)Mo(CO)4] or [(cod)PdCl2] (nor = norbornadiene, cod = cycloocta‐1,8‐diene). Attempts to prepare 1,8‐diphosphinonaphthalene ( 7 ) by reducing 2 or 3 with LiAlH4 or LiAlH4/TMSCl (1 : 1) (TMSCl = trimethyl chlorosilane) in THF led to inseparable mixtures of phosphorus‐containing products. Compounds 2 – 6 were characterised by 1H‐, 13C‐, and 31P‐NMR spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis. X‐ray crystal structure analyses were carried out for the bis‐phosphonate anhydride rac‐ 4 and the palladium(II) complex 6 . The geometry of compound rac‐ 4 , in which the phosphorus atoms are connected by an oxygen atom, reveals a relief of strain from the bis‐phosphine 1 , whereas the 1,8‐P,P′‐naphthalenediyl group in 6 is surprisingly distorted; the P atoms are displaced from the naphthalene best plane by –46.7 and 54.5 pm. 相似文献
20.
Exploring Bis(cyclometalated) Ruthenium(II) Complexes as Active Catalyst Precursors: Room‐Temperature Alkene–Alkyne Coupling for 1,3‐Diene Synthesis
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Jing Zhang Dr. Angel Ugrinov Prof. Dr. Yong Zhang Prof. Dr. Pinjing Zhao 《Angewandte Chemie (International ed. in English)》2014,53(32):8437-8440
Described is the development of a new class of bis(cyclometalated) ruthenium(II) catalyst precursors for C? C coupling reactions between alkene and alkyne substrates. The complex [(cod)Ru(3‐methallyl)2] reacts with benzophenone imine or benzophenone in a 1:2 ratio to form bis(cyclometalated) ruthenium(II) complexes ( 1 ). The imine‐ligated complex 1 a promoted room‐temperature coupling between acrylic esters and amides with internal alkynes to form 1,3‐diene products. A proposed catalytic cycle involves C? C bond formation by oxidative cyclization, β‐hydride elimination, and C? H bond reductive elimination. This RuII/RuIV pathway is consistent with the observed catalytic reactivity of 1 a for mild tail‐to‐tail methyl acrylate dimerization and for cyclobutene formation by [2+2] norbornene/alkyne cycloaddition. 相似文献