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1.
Jana Maderov Jaromír Marek Frantiek Pavel
ík 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(5):m178-m180
The mononuclear title complex, [Co(C6H6NO6)(C2H8N2)]·3H2O, contains an octahedrally coordinated CoIII atom. The N‐(carboxymethyl)aspartate moiety is coordinated as a tetradentate ligand, providing an OONO‐donor set and forming two trans five‐membered chelate rings and one six‐membered chelate ring. A seven‐membered chelate ring is also formed, which consists of part of the six‐membered chelate ring and part of one of the five‐membered chelate rings. The crystal structure of the complex is stabilized by hydrogen bonds with three water molecules. 相似文献
2.
Treatment of Pd(PPh3)4 with 5‐bromo‐pyrimidine [C4H3N2Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh3)2(η1‐C4H3N2)(Br)], 1 , by substituting two triphenylphosphine ligands. In acetonitrile solution of 1 in refluxing temperature for 1 day, it do not undergo displacement of the triphenylphosphine ligand to form the dipalladium complex [Pd(PPh3)Br]2{μ,η2‐(η1‐C4H3N2)}2, or bromide ligand to form chelating pyrimidine complex [Pd(PPh3)2(η2‐C4H3N2)]Br. Complex 1 reacted with bidentate ligand, NH4S2CNC4H8, and tridentate ligand, KTp {Tp = tris(pyrazoyl‐1‐yl)borate}, to obtain the η2‐dithiocarbamate η1‐pyrimidine complex [Pd(PPh3)(η1‐C4H3N2)(η2‐S2CNC4H8)], 4 and η2‐Tp η1‐pyrimidine complex [Pd(PPh3)(η1‐C4H3N2)(η2‐Tp)], 5 , respectively. Complexes 4 and 5 are characterized by X‐ray diffraction analyses. 相似文献
3.
Roberto Centore Antonio Roviello Angela Tuzi Barbara Panunzi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):m26-m28
The title compounds, {5‐(dimethylamino)‐2‐[N‐(4‐methoxyphenyl)iminomethyl]phenyl}[N‐(4‐methoxyphenyl)‐4‐nitrosalicylaldiminato]palladium(II), [Pd(C14H11N2O4)(C16H17N2O)], (I), and [4‐(diethylamino)‐N‐(4‐methoxyphenyl)salicylaldiminato]{2‐[N‐(4‐methoxyphenyl)iminomethyl]‐5‐nitrophenyl}palladium(II) dichloromethane hemisolvate, [Pd(C14H11N2O3)(C18H21N2O2)]·0.5CH2Cl2, (II), both contain push–pull chromophores coordinated to Pd in a square‐planar arrangement. In both compounds, the five‐membered orthopalladated ring is essentially planar, while the coordinated six‐membered ring is not. Deviations from a coplanar arrangement of the phenylene rings of the coordinated Schiff bases are observed in both (I) and (II) as a result of intramolecular steric interactions. 相似文献
4.
The coordination chemistry of platinum(II) with a series of thiosemicarbazones {R(H)C2=N3‐N2(H)‐C1(=S)‐N1H2, R = 2‐hydroxyphenyl, H2stsc; pyrrole, H2ptsc; phenyl, Hbtsc} is described. Reactions of trans‐PtCl2(PPh3)2 precursor with H2stsc (or H2ptsc) in 1 : 1 molar ratio in the presence of Et3N base yielded complexes, [Pt(η3‐ O, N3, S‐stsc)(PPh3)] ( 1 ) and [Pt(η3‐ N4, N3, S‐ptsc)(PPh3)] ( 2 ), respectively. Further, trans‐PtCl2(PPh3)2 and Hbtsc in 1 : 2 (M : L) molar ratio yielded a different compound, [Pt(η2‐ N3, S‐btsc)(η1‐S‐btsc)(PPh3)] ( 3 ). Complex 1 involved deprotonation of hydrazinic (‐N2H‐) and hydroxyl (‐OH) groups, and stsc2? is coordinating via O, N3, S donor atoms, while complex 2 involved deprotonation of hydrazinic (‐N2H‐) and ‐N4H groups and ptsc2? is probably coordinating via N4, N3, S donor atoms. Reaction of PdCl2(PPh3)2 with Hbtsc‐Me {C6H5(CH3)C2=N3‐N2(H)‐C1(=S)‐N1H2} yielded a cyclometallated complex [Pd(η3‐C, N3, S‐btsc‐Me)(PPh3)] ( 4 ). These complexes have been characterized with the help of analytical data, spectroscopic techniques {IR, NMR (1H, 31P), U.V} and single crystal X‐ray crystallography ( 1 , 3 and 4 ). The effects of substituents at C2 carbon of thiosemicarbazones on their dentacy and cyclometallation are emphasized. 相似文献
5.
Three new oxime‐based palladacycles, namely [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(dppm)]ClO4 ( 1 ), [Pd2{C,N‐C6H4{C(Me)?NOH}‐2}2(dppe)2(μ‐dppe)](ClO4)2 ( 2 ) and [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(dppmS2)]ClO4 ( 3 ), were synthesized by the reaction of dinuclear oxime complex [Pd{C,N‐C6H4{C(Me)?NOH}‐2}(μ‐Cl)]2 with different diphosphine ligands (dppm, dppe and dppmS2). The synthesized complexes were characterized using Fourier transform infrared, 31P NMR, 1H NMR and 13C NMR spectroscopic methods and elemental analyses, and their molecular structures were elucidated using X‐ray crystallography. The structure of 2 is worthy of note as it is the first oxime palladacycle where there are both bridging (P–) and chelating (P^P) dppe ligands, giving rise to a dinuclear complex. The palladium atom is in a five‐coordinate, square pyramidal P3NC environment, while in 3 the palladium atom is in a distorted square planar environment, coordinated by the oxime ligand and a chelating (S^S) dppmS2 ligand. These complexes were employed as efficient catalysts for the Suzuki–Miyaura cross‐coupling reaction of several aryl bromides with phenylboronic acid. The in vitro cytotoxicity of the compounds was also evaluated against human tumour cell lines (HT29, A549 and HeLa) using the MTT assay method. The results indicate that the dinuclear complex 2 has greater catalytic and anticancer activity in comparison with the mononuclear complexes 1 and 3 . 相似文献
6.
Holger Braunschweig Michael Burzler Rian D. Dewhurst Krzysztof Radacki Fabian Seeler 《无机化学与普通化学杂志》2008,634(11):1875-1879
The dimanganese bridging borylene complex [μ‐BMes {(η5‐C5H4Me)Mn(CO)2}2] was synthesized from Mes(Cl)BB(Cl)Mes and K[(η5‐C5H4Me)Mn(CO)2H] at low temperature, providing a small sample after manual separation of crystals, allowing a perfunctory spectroscopic analysis, but affording conclusive X‐ray crystallographic structural data. The trimetallic bridging borylene complex [(μ3‐BCl){{(η5‐C5H4Me)Mn(CO)2} {Pd(PCy3)}2}] was prepared by the addition of [Pd(PCy3)2] to a solution of [μ‐BCl{(η5‐C5H4Me)Mn(CO)2}2], affording pure crystals that were fully characterised including X‐ray crystallographic analysis. The structure is reconciled with detailed theoretical analysis for related model complexes, [(μ3‐BX){{(η5‐C5H5)Mn(CO)2}{Pd(PMe3)}2}] (X = Me, Cl). 相似文献
7.
Katherine A. Bussey Annie R. Cavalier Jennifer R. Connell Margaret E. Mraz Kayode D. Oshin Tomislav Pintauer Allen G. Oliver 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):526-533
The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the CuI and CuII oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena‐poly[[copper(I)‐μ2‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ5N,N′,N′′:C2,C3] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two CuI complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the CuI atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with CuII show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu2Cl2 moiety. 相似文献
8.
Prof. Dr. Wolfram W. Seidel Woldemar Dachtler Julia Semmler Marco Tänzler Manuel Folk Dr. Alexander Villinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14702-14711
A series of heterodinuclear complexes with acetylene dithiolate (acdt2?) as the bridging moiety were synthesised by a facile one‐pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W–Ru complex [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] (Tp’=hydrotris(3,5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C2S2)Pd(dppe)] and [Tp′W(CO)2(C2S2)Pd(dppe)][PF6] (dppe=1,2‐bis(diphenylphoshino)ethane), which exhibit a [W(η2‐κ2‐C2S2)M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me3Si‐ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W–Ru complex [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO)2(C2S2)Ru(η5‐C5H5)(PPh3)][PF6]. Single crystal X‐ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt2? linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt2? in [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] relative to [Tp′W(CO)2(C2S2)Ru(η5‐C5H5)(PPh3)]+. In addition, the influence of the overall complex charge on the metric parameters was investigated by single‐crystal X‐ray diffraction studies with the W–Pd complexes [Tp′WL2(C2S2)Pd(dppe)] (L=(CN?)(CO) or (CO)2). The central [W(C2S2)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals. 相似文献
9.
Magno Agostinho Andrei Banu Pierre Braunstein Richard Welter Xavier Morise 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(3):m81-m86
Three new palladium complexes containing a difunctional P,N‐chelate, namely tris(chloro{[1‐methyl‐1‐(6‐methyl‐2‐pyridyl)ethoxy]diphenylphospine‐κ2N,P}methylpalladium(II)chloroform solvate, 3[Pd(CH3)Cl(C21H22NOP)]·CHCl3, (III), dichloro[2‐(2,6‐dimethylphenyl)‐6‐(diphenylphosphinomethyl)pyridine‐κ2N,P]palladium(II), [PdCl2(C26H24NP)], (IV), and chloro[2‐(2,6‐dimethylphenyl)‐6‐(diphenylphosphinomethyl)pyridine‐κ2N,P]methylpalladium(II), [Pd(CH3)Cl(C26H24NP)], (V), are reported. Geometric data and the conformations of the ligands around the metal centers, as well as slight distortions of the Pd coordination environments from idealized square‐planar geometry, are discussed and compared with the situations in related compounds. Non‐conventional hydrogen‐bond interactions (C—H⋯Cl) have been found in all three complexes. Compound (III) is the first six‐membered chloro–methyl–phosphinite P,N‐type PdII complex to be structurally characterized. 相似文献
10.
Miao Du Zhi‐Liang Shang Qiang Xu Ruo‐Hua Zhang Xue‐Bing Leng Xian‐He Bu 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(7):769-770
The crystal structure of the title compound, [CoCl‐(C16H26N6)]ClO4, consists of discrete [CoCl(C16H26N6)]+ cations and perchlorate anions. The five‐coordinate CoII atom has four nitrogen donors from the new mesocyclic ligand 1,5‐bis(1‐methyl‐1H‐imidazol‐2‐ylmethyl)‐1,5‐diazacyclooctane [Co—N 2.046 (3)–2.214 (4) Å], and a chloride anion at the apical site [Co—Cl 2.3184 (13) Å]. The coordination geometry of the complex is essentially square pyramidal. The mesocyclic ligand takes a boat–chair configuration and the two imidazole pendants are not coplanar. The dihedral angle between the two imidazole planes is 15.97°. An H atom from the 1,5‐diazacyclooctane group effectively blocks the axial coordination site opposite the Cl ligand. 相似文献
11.
Dinuclear Palladium Complexes with Two Ligand‐Centered Radicals and a Single Bridging Ligand: Subtle Tuning of Magnetic Properties 下载免费PDF全文
M. Sc. Daniël L. J. Broere Dr. Serhiy Demeshko Prof. Dr. Bas de Bruin Dr. Evgeny A. Pidko Prof. Dr. Joost N. H. Reek Dr. Maxime A. Siegler Dr. Martin Lutz Dr. Jarl Ivar van der Vlugt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5879-5886
The facile and tunable preparation of unique dinuclear [(L?)Pd?X?Pd(L?)] complexes (X=Cl or N3), bearing a ligand radical on each Pd, is disclosed, as well as their magnetochemistry in solution and solid state is reported. Chloride abstraction from [PdCl( NNOISQ )] ( NNOISQ =iminosemiquinonato) with TlPF6 results in an unusual monochlorido‐bridged dinuclear open‐shell diradical species, [{Pd( NNO ISQ)}2(μ‐Cl)]+, with an unusually small Pd‐Cl‐Pd angle (ca. 93°, determined by X‐ray). This suggests an intramolecular d8–d8 interaction, which is supported by DFT calculations. SQUID measurements indicate moderate antiferromagnetic spin exchange between the two ligand radicals and an overall singlet ground state in the solid state. VT EPR spectroscopy shows a transient signal corresponding to a triplet state between 20 and 60 K. Complex 2 reacts with PPh3 to generate [Pd(NNOISQ)(PPh3)]+ and one equivalent of [PdCl( NNOISQ )]. Reacting an 1:1 mixture of [PdCl( NNOISQ )] and [Pd(N3)( NNOI SQ)] furnishes the 1,1‐azido‐bridged dinuclear diradical [{Pd( NNO ISQ)}2(κ1‐N;μ‐N3]+, with a Pd‐N‐Pd angle close to 127° (X‐ray). Magnetic and EPR measurements indicate two independent S=1/2 spin carriers and no magnetic interaction in the solid state. The two diradical species both show no spin exchange in solution, likely because of unhindered rotation around the Pd?X?Pd core. This work demonstrates that a single bridging atom can induce subtle and tunable changes in structural and magnetic properties of novel dinuclear Pd complexes featuring two ligand‐based radicals. 相似文献
12.
Enantioselective Synthesis of Pyrrole‐Based Spiro‐ and Polycyclic Derivatives by Iridium‐Catalyzed Asymmetric Allylic Dearomatization and Controllable Migration Reactions 下载免费PDF全文
Dr. Chun‐Xiang Zhuo Qiang Cheng Dr. Wen‐Bo Liu Qiang Zhao Prof. Dr. Shu‐Li You 《Angewandte Chemie (International ed. in English)》2015,54(29):8475-8479
The first highly diastereo‐ and enantioselective synthesis of five‐membered spiro‐2H‐pyrroles was achieved using an Ir‐catalyzed asymmetric allylic dearomatization reaction. The spiro‐2H‐pyrrole derivatives readily undergo a controllable and stereospecific allylic migration under acid catalysis, providing polycyclic pyrrole derivatives in excellent yields and ee values. Additionally, the novel Ir‐complex K1 , derived from [Ir(cod)Cl]2 (cod=1,5‐cyclooctadiene) and N‐benzhydryl‐N‐phenyldinaphthophosphoramidite (BHPphos), showed excellent control of both diastereo‐ and enantioselectivities. 相似文献
13.
Namk
zdemir Muharrem Diner Osman Dayan Bekir etinkaya 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):m407-m409
In the title compound, [RuCl2(C2H3N)(C27H31N3)]·CH2Cl2, the RuII ion is six‐coordinated in a distorted octahedral arrangement, with the two Cl atoms located in the apical positions, and the pyridine (py) N atom, the two imino N atoms and the acetonitrile N atom located in the basal plane. The two equatorial Ru—Nimino distances are almost equal (mean 2.087 Å) and are substantially longer than the equatorial Ru—Npy bond [1.921 (4) Å]. It is observed that the Nimino—M—Npy angle for the five‐membered chelate rings of pyridine‐2,6‐diimine complexes is inversely related to the magnitude of the M—Npy bond. The title structure is stabilized by intra‐ and intermolecular C—H...Cl hydrogen bonds, as well as by van der Waals interactions. 相似文献
14.
Min‐Shiun Chao Horng‐Hwa Lu Ming‐Liao Tsai Tsung‐Hsuan Hsieh Chien‐Min Lin 《中国化学会会志》2009,56(5):916-922
The self‐assembly of Co(II) with two diaminodiamide ligands, 4,7‐diazadecanediamide and 4,8‐diazaundecanediamide, gave two different crystals, [(C8H18N4O2)Co(OH)2Co(C8H18N4O2)]Cl2 ( 1 ) [Co(C9H20N4O2)(Cl)(H2O)]·Cl·2H2O ( 2 ). Structures of 1 and 2 were characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 shows a novel type of binuclear complex with distorted octahederal coordination geometry around the Co atoms through the hydroxo bridges. By using inter‐connector N‐H···N hydrogen bonding interactions as building forces, each cationic moiety [(C8H18N4O2)Co(OH)2Co(C8H18N4O2)]2+ is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chain‐like structure. The chains are further connected into a 2D layer in a (4,4)‐topology via N‐H···Clfree hydrogen‐bonding interactions. Structural data for 2 indicate that the cobalt atom adopts a six‐coordinated N2O4 environment, giving a distorted octahedral geometry, where two N‐ and two O‐donor sets of ligand located at equatorial positions and one water and one chloride occupied at axial positions. Through NH···Cl‐Co and OH···Cl‐Co contacts, each cationic moiety [Co(C9H20N4O2)(Cl)(H2O)]+ in 2 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thus, the crystal‐engineering approach has proved successful in the solid‐state packing due to steric strain effect of the diaminodiamide ligand. 相似文献
15.
B. Rke F. Zülch Y. Ding J. Prust H. W. Roesky M. Noltemeyer H.‐G. Schmidt 《无机化学与普通化学杂志》2001,627(5):836-840
Synthesis, Structure, and Properties of [nacnac]MX3 Compounds (M = Ge, Sn; X = Cl, Br, I) Reactions of [nacnac]Li [(2,6‐iPr2C6H3)NC(Me)C(H)C(Me)N(2,6‐iPr2C6H3)]Li ( 1 ) with SnX4 (X = Cl, Br, I) and GeCl4 in Et2O resulted in metallacyclic compounds with different structural moieties. In the [nacnac]SnX3 compounds (X = Cl 2 , Br 3 , I 4 ) the tin atom is five coordinated and part of a six‐membered ring. The Sn–N‐bond length of 3 is 2.163(4) Å and 2.176(5) Å of 4 . The five coordinated germanium of the [nacnac]GeCl3 compound 5 shows in addition to the three chlorine atoms further bonds to a carbon and to a nitrogen atom. In contrast to the known compounds with the [nacnac] ligand the afore mentioned reaction creates a carbon–metal‐bond (1.971(3) Å) forming a four‐membered ring. The Ge–N bond length (2.419(2) Å) indicates the formation of a weakly coordinating bond. 相似文献
16.
Ming Zhang Xiaoli Liu Chaojun Shi Chunxia Ren Yuqiang Ding Herbert W. Roesky 《无机化学与普通化学杂志》2008,634(10):1755-1758
Treatment of N‐heterocyclic silylene Si[N(tBu)CH]2 ( 1 ) and [(η3‐C3H5)PdCl]2 in toluene led to the formation of the mononuclear complex (η3‐C3H5)Pd{Si[N(tBu)CH]2}Cl ( 3 ), the silicon analogue to N‐heterocyclic carbene complex (η3‐C3H5)Pd{C[N(tBu)CH]2}Cl ( 2 ). Complex 3 was characterized with 1H NMR and 13C NMR. Investigation shows that (η3‐C3H5)Pd{Si[N(tBu)CH]2}Cl is an active catalyst for Heck coupling reaction of styrene with aryl bromides. 相似文献
17.
Cristiano Zuccaccia Gianfranco Bellachioma Giuseppe Cardaci Alceo Macchioni Barbara Binotti Carla Carfagna 《Helvetica chimica acta》2006,89(8):1524-1546
Palladacyclic compounds [Pd(C6H4(C6H5C?O)C?N? R)(N? N)] [X] (R = Et, iPr, 2,6‐iPr2C6H3; N? N = bpy = 2,2′‐bipyridine, or 1,4‐(o,o′‐dialkylaryl)‐1,4‐diazabuta‐1,3‐dienes; [X]? = [BF4]? or [PF6]?) were synthesized from the dimers [{Pd(C6H4(C6H5C?O)C?N? R)(μ‐Cl)}2] and N? N ligands. Their interionic structure in CD2Cl2 was determined by means of 19F,1H‐HOESY experiments and compared with that in the solid state derived from X‐ray single‐crystal studies. [Pd(C6H4(C6H5C?O)C?N? R)(N? N)] [X] complexes were found to copolymerize CO and p‐methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4‐(o,o′‐dimethylaryl)‐1,4‐diazabuta‐1,3‐dienes were used, respectively. The reactions with CO and p‐methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the Pd? C bonds were isolated and completely characterized in solution. 相似文献
18.
Kai Liang Yi‐Zhi Li He‐Gen Zheng Xin‐Quan Xin 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(8):m310-m312
In the title compound, [1,4‐bis(diphenylphosphino)butane‐2κ2P,P′]di‐μ‐thio‐1:2κ4S‐dithio‐1κ2S‐palladium(II)tungsten(VI) N,N′‐dimethylformamide hemisolvate hemihydrate, [PdWS4(C28H28P2)]·0.5C3H7NO·0.5H2O, the Pd atom is coordinated by two S atoms from the distorted‐tetrahedral [WS4]2− anion and two P atoms from the dppb molecule [dppb is 1,4‐bis(diphenylphosphino)butane] in an approximately square‐planar configuration. A puckered seven‐membered ring is formed by the Pd atom and the dppb ligand. 相似文献
19.
Leszek Pazderski Tomasz Pawlak Jerzy Sitkowski Lech Kozerski Edward Szłyk 《Magnetic resonance in chemistry : MRC》2009,47(11):932-941
1H, 13C, 15N and 195Pt NMR studies of gold(III) and platinum(II) chloride organometallics with N(1),C(2′)‐chelated, deprotonated 2‐phenylpyridine (2ppy*) of the formulae [Au(2ppy*)Cl2], trans(N,N)‐[Pt(2ppy*)(2ppy)Cl] and trans(S,N)‐[Pt(2ppy*)(DMSO‐d6)Cl] (formed in situ upon dissolving [Pt(2ppy*)(µ‐Cl)]2 in DMSO‐d6) were performed. All signals were unambiguously assigned by HMBC/HSQC methods and the respective 1H, 13C and 15N coordination shifts (i.e. differences between chemical shifts of the same atom in the complex and ligand molecules: Δ1Hcoord = δ1Hcomplex ? δ1Hligand, Δ13Ccoord = δ13Ccomplex ? δ13Cligand, Δ15Ncoord = δ15Ncomplex ? δ15Nligand), as well as 195Pt chemical shifts and 1H‐195Pt coupling constants discussed in relation to the known molecular structures. Characteristic deshielding of nitrogen‐adjacent H(6) protons and metallated C(2′) atoms as well as significant shielding of coordinated N(1) nitrogens is discussed in respect to a large set of literature NMR data available for related cyclometallated compounds. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
20.
Photochemical Reactions of Cyclopentadienylbis(ethene)rhodium with Benzene Derivatives During UV irradiation of [CpRh(C2H4)2] ( 1 ) (Cp = η5‐C5H5) in hexane in the presence of hexamethylbenzene the di‐ and trinuclear arene bridged complexes [(CpRh)2(μ‐η3 : η3‐C6Me6)] ( 3 ) and [(CpRh)3(μ3‐η2 : η2 : η2‐C6Me6)] ( 4 ) are formed besides known [CpRh(η4‐C6Me6)] ( 2 ). It was shown by a separate experiment that 3 besides small amounts of 4 is formed by attack of photochemically from 1 arising CpRh fragments at the free double bond of the η4‐bonded benzene ring in 2 . Irradiation of 1 in the presence of diphenyl (C12H10) affords the compounds [(CpRh)2(μ‐η3 : η3‐C12H10)] ( 5 ) and [(CpRh)3(μ3‐η2 : η2 : η2‐C12H10)] ( 6 ) as analogues of 3 and 4 , in the presence of triptycene (C20H14) only [(CpRh)2(μ‐η3 : η3‐C20H14)] ( 7 ) is obtained; the bridging in 5 , 6 , and 7 always occurs via the same six‐membered ring of the corresponding ligand system. During the photochemical reaction of 1 in the presence of styrene (C8H8) substitution of the ethene ligands by the vinyl groups with formation of [CpRh(C2H4)(η2‐C8H8)] ( 8 ) and known [CpRh(η2‐C8H8)2] ( 9 ) is observed exclusively. The new complexes were characterized analytically and spectroscopically, in the case of 3 also by X‐ray structure analysis. 相似文献