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1.
Wioletta Bendziska‐Berus Magdalena Kaik‐King Gary King Urszula Rychlewska 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(12):1174-1177
In connection with a research program involving the synthesis, structure determination, reactivity and ability to coordinate to metal centres of chiral bisphosphine ligands, we have synthesized and structurally characterized, by means of single‐crystal X‐ray diffraction analysis, the title compound {systematic name: (S,S)‐(ethane‐1,2‐diyl)bis[(2‐methylphenyl)phenylphosphane], abbreviated as o‐tolyl‐DiPAMP}, C28H28P2. So far, neither the free bisphosphine (DiPAMP) nor analogues that incorporate the ethylenebisphosphine frame have had their crystal structures reported. The investigated compound forms crystals which are isostructural with the bisphosphine dioxide analogue [King et al. (2007). Acta Cryst. E 63 , o3278], despite the involvement of the dioxide in C—H...O(=P) hydrogen bonds and the lack of similar hydrogen bonds in the investigated crystal structure. In both molecules, the P—C—C—P chain is in a trans conformation, extended further at both ends by one of the two P—Cipso bonds. The planes of the phenyl and o‐tolyl rings attached to the same P atom are nearly perpendicular to one another. Both crystal structures are mainly stabilized by dispersive interactions. 相似文献
2.
Farhad Haghjoo Nick Barnes Robin Pritchard 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(7):o219-o221
In the crystal structure of the title compound, 2C22H24P+·I82−, the I82− anion is located on a crystallographic inversion centre and consists of two tri‐iodide anions linked by di‐iodine at angles of 89.92 (4)° to form a planar `Z'‐shaped dianion. The octaiodides are linked via long‐range interactions [3.877 (11) Å] into infinite polyiodide ribbons. This is the first example of a structure containing an [(o‐tolyl)3PMe]+ cation, and the CMe—P—C—CMe torsion angles of −54.0 (11), −51.3 (11) and −48.2 (11)° indicate that the configuration is exo3. 相似文献
3.
The dialkyl compound cis‐dimethyl[(sulfinyl‐κS)bis[methane]][tris(2‐methylphenyl)phosphine]platinum(2+) (cis‐[Pt(Me)2(dmso)(P(o‐tol)3]; 1 ) has been isolated from the reaction of cis‐dimethylbis[(sulfinyl‐κS)bis[methane]]platinum(2+) (cis‐[Pt(Me)2(dmso)2]) with tris(2‐methylphenyl)phosphane (P(o‐tol)3). Restricted rotation around the P? Cipso bonds of the phosphane ligand generates two different conformers, 1a and 1b , in rapid exchange in non‐polar solvents at low temperature. Strong through‐space contacts between the ortho‐Me substituent groups on the ligand and the cis‐Me groups in the coordination plane were determined, which proved useful for identifying the atropisomers formed. At room temperature, 1H‐NMR spectra of 1 maintain a ‘static’ pattern upon onset of easy and rapid ortho‐platination, leading to [[2‐[bis(2‐methylphenyl)phosphino‐κP]phenyl]methyl‐κC]methyl[(sulfinyl‐κS)bis[methane]]platinum(2+) ( 2 ), a new C,P‐cyclometalated compound of platinum(II), with liberation of methane. The process has been studied by 1H‐ and 31P{1H}‐NMR in CDCl3, and kinetics experiments were performed by conventional spectrophotometric techniques. The first‐order rate constants kc decrease with the addition of dimethyl sulfoxide until the process is blocked by the presence of a sufficient excess of sulfoxide. This behavior reveals a mechanism initiated by ligand dissociation and formation of a three‐coordinate species. The value of the rate constant for dimethyl sulfoxide dissociation k1 has been measured independently over a wide temperature range by both 1H‐NMR ligand exchange (isotopic labeling experiments) and ligand substitution (stopped‐flow pyridine for dimethyl sulfoxide substitution). The rates of the two processes are in reasonable agreement at the same temperature, and a single Eyring plot can be constructed with the two sets of kinetics data. However, the value of the derived dissociation constant at 308 K (k1=6.5±0.3 s?1) is at least two orders of magnitude higher than that of cyclometalation (kc=0.0098±0.0009 s?1 at 308 K). Clearly, the dissociation step is not rate‐determining for cyclometalation. A multistep mechanism consistent with mass‐law retardation is derived, which involves a pre‐equilibrium that controls the concentration of an unsaturated three‐coordinate, 14‐electron T‐shaped cis‐[PtMe2{P(o‐tol)3}] intermediate. Cyclometalation is initiated in this latter by an agostic interaction with the σ(C? H) orbital of a methyl group. Oxidative addition of the C? H bond follows, yielding a cyclometalated‐hydrido 16‐electron Pt(IV) five‐coordinate intermediate. Finally, reductive elimination and re‐entry of dimethyl sulfoxide with liberation of methane should yield the cyclometalated species 2 . 相似文献
4.
John Nicolson Low Justo Cobo Braulio Insuasty Manuel Nogueras Angela Salcedo Adolfo Snchez 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):o125-o128
The title compounds, 2‐(4‐bromophenyl)‐1,2‐dihydropyrimido[1,2‐a]benzimidazol‐4‐(3H)‐one, C16H12BrN3O, (IVa), and 4‐(4‐methylphenyl)‐3,4‐dihydropyrimido[1,2‐a]benzimidazol‐2‐(1H)‐one, C17H15N3O, (Vb), both form R(8) centrosymmetric dimers via N—H?N hydrogen bonds. The N?N distance is 2.943 (3) Å for (IVa) and 2.8481 (16) Å for (Vb), with the corresponding N—H?N angles being 129 and 167°, respectively. However, in other respects, the supramolecular structures of the two compounds differ. Both compounds contain different C—H?π interactions, in which the C—H?π(centroid) distances are 2.59 and 2.47 Å for (IVa) and (Vb), respectively (the latter being a short distance), with C—H?π(centroid) angles of 158 and 159°, respectively. The supramolecular structures also differ, with a short Br?O distance of 3.117 (2) Å in bromo derivative (IVa), and a C—H?O interaction with a C?O distance of 3.2561 (19) Å and a C—H?O angle of 127° in tolyl system (Vb). The dihydropyrimido part of (Vb) is disordered, with a ratio of the major and minor components of 0.9:0.1. The disorder consists of two non‐interchangeable envelope conformers, each with an equatorial tolyl group and an axial methine H atom. 相似文献
5.
Phosphanediyl Transfer from Inversely Polarized Phosphaalkenes R1P=C(NMe2)2 (R1 = tBu, Cy, Ph, H) onto Phosphenium Complexes [(η5‐C5H5)(CO)2M=P(R2)R3] (R2 = R3 = Ph; R2 = tBu, R3 = H; R2 = Ph, R3 = N(SiMe3)2) Reaction of the freshly prepared phosphenium tungsten complex [(η5‐C5H5)(CO)2W=PPh2] ( 3 ) with the inversely polarized phosphaalkenes RP=C(NMe2)2 ( 1 ) ( a : R = tBu; b : Cy; c : Ph) led to the η2‐diphosphanyl complexes ( 9a‐c ) which were isolated by column chromatography as yellow crystals in 24‐30 % yield. Similarly, phosphenium complexes [(η5‐C5H5)(CO)2M=P(H)tBu] (M = W ( 6 ); Mo ( 8 )) were converted into (M = W ( 11 ); Mo ( 12 )) by the formal abstraction of the phosphanediyl [PtBu] from 1a . Treatment of [(η5‐C5H5)(CO)2W=P(Ph)N(SiMe3)2] ( 4 ) with HP=C(NMe2)2 ( 1d ) gave rise to the formation of yellow crystalline ( 10 ). The products were characterized by elemental analyses and spectra (IR, 1H, 13C‐, 31P‐NMR, MS). The molecular structure of compound 10 was elucidated by an X‐ray diffraction analysis. 相似文献
6.
Jorge Trilleras Jairo Quiroga Justo Cobo Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(1):o11-o14
2‐Amino‐4‐chloro‐5‐formyl‐6‐[methyl(2‐methylphenyl)amino]pyrimidine, C13H13ClN4O, (I), and 2‐amino‐4‐chloro‐5‐formyl‐6‐[(2‐methoxyphenyl)methylamino]pyrimidine, C13H13ClN4O2, (II), are isostructural and essentially isomorphous. Although the pyrimidine rings in each compound are planar, the ring‐substituent atoms show significant displacements from this plane, and the bond distances provide evidence for polarization of the electronic structures. In each compound, a combination of N—H...N and N—H...O hydrogen bonds links the molecules into sheets built from centrosymmetric R22(8) and R66(32) rings. The significance of this study lies in its observation of the isostructural nature of (I) and (II), and in the comparison of their crystal and molecular structures with those of analogous compounds. 相似文献
7.
Alison J. Edwards Eric Wenger 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m230-m231
The crystal and molecular structures of the title compound, 3‐bromo‐3‐(dibenzylphenylphosphonio)‐2,2‐diphenyl‐5‐trifluoromethyl‐1H‐benzo[e][1,2]phosphanickelepine, [NiBr(C22H17F3P)(C20H19P)], which was obtained as the major regioisomer from insertion of HCCCF3 into the Ni—C bond of the five‐membered phosphanickelacycle [NiBr(o‐C6H4CH2PPh2‐κ2C,P){PPh(CH2Ph)2}], have been determined. Principal geometric data include the Ni—X bond lengths Ni—Br 2.3343 (4) Å, Ni—P 2.1867 (7) and 2.2094 (7) Å, and Ni—C 1.882 (3) Å, and the two trans angles P—Ni—P 171.55 (3)° and Br—Ni—C 176.88 (9)°. 相似文献
8.
Vasu K. A. Nirmala A. R. Choudhury S. Mohan J. Saravanan T. Narasimhamurthy 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(12):o676-o678
The two title compounds, 2‐({(1Z)‐[4‐(dimethylamino)phenyl]methylene}amino)‐4,5‐dimethyl‐N‐(2‐methylphenyl)thiophene‐3‐carboxamide, C23H25N3OS, (I), and 2‐({(1E)‐[4‐(dimethylamino)phenyl]methylene}amino)‐N‐(4‐methylphenyl)‐4,5,6,7‐tetrahydro‐1‐benzothiophene‐3‐carboxamide,C25H27N3OS, (II), show antibacterial and antifungal activities. The asymmetric unit of (II) contains two crystallographically independent molecules. The o‐toluidine ring in (I) lies gauche with respect to the thiophene ring. In (II), the p‐toluidine ring is coplanar with the thiophene ring in one molecule, but is tilted from it in the other molecule. Neither structure exhibits any significant intermolecular interactions, but in both, an intramolecular N—H⋯N hydrogen bond forms a pseudo‐six‐membered ring, thus locking the molecular conformation and removing conformational flexibility. 相似文献
9.
Synthesis and Characterization of Manganese(I) Carbonyl Complexes of the Type [(OC)4Mn{μ‐P(R)Aryl}]2
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Metalation of secondary phosphanes HPRR′ [R = R′ = C6H4‐4‐Me, C6H3‐3,5‐Me2 ( 3 ), C6H4‐4‐NMe2 ( 4 ); R/R′ = Ph/cHex] with Mn2(CO)10 in boiling xylene (mixture of isomers), until the evolution of gaseous carbon monoxide ceases, leads to the formation of the dinuclear complexes of the type [(OC)4Mn(μ‐PRR′)]2 [R = R′ = C6H4‐4‐Me ( 5 ), C6H3‐3,5‐Me2 ( 6 ), R/R′ = Ph/cHex ( 7 ), R = R′ = C6H4‐4‐NMe2 ( 8 )] with poor to moderate yields. These manganese(I) complexes are only sparingly soluble or even nearly insoluble in hydrocarbons at room temperature. Planar four‐membered Mn2P2 rings represent the central moiety with four carbonyl ligands at each manganese(I) atom. The steric demand of the P‐bound substituents influences the Mn–P bond lengths as well as the P–Mn–P bond angles. 相似文献
10.
Christopher Glidewell John N. Low Manuel Melguizo Antonio Quesada 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(4):o202-o204
Molecules of the title compound, C6H9N3O2, are linked by an N—H⃛O hydrogen bond [H⃛O = 2.29 Å, N⃛O = 3.169 (2) Å and N—H⃛O = 173°] and an N—H⃛N hydrogen bond [H⃛N = 2.12 Å, N⃛N = 2.999 (2) Å and N—H⃛N = 175°] into sheets containing centrosymmetric R(8) and R(28) rings; the sheets are reinforced by a single aromatic π–π‐stacking interaction. 相似文献
11.
Natalia G. Petrochko R. Gregory Peters Russell G. Baughman 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(5):508-511
The crystal structures of the title compounds, [Mo{(C4H8NO)2P(C2F5)}(CO)5], (1a), and [Mo{(C5H10N)2P(C2F5)}(CO)5], (2a), were determined as part of a larger project that focuses on the synthesis and coordination chemistry of phosphane ligands possessing moderate (electroneutral, i.e. neither electron‐rich nor electron‐deficient) electronic characteristics. Both complexes feature a slightly distorted octahedral geometry at the metal center, due to the electronic and steric repulsions between two of the four equatorial CO groups and the pentafluoroethyl group attached to the phosphane ligand. Bond length and angle data for (1a) and (2a) support the conclusion that the free phosphane ligands are electroneutral. For complex (1a), the Mo—P, Mo—Cax and Mo—Ceq(ave) bond lengths are 2.5063 (5), 2.018 (2) and 2.048 (2) Å, respectively, and for complex (2a) these values are 2.5274 (5), 2.009 (3) and 2.050 (3) Å, respectively. Geometric data for (1a) and (2a) are compared with similar data reported for analogous Mo(CO)5 complexes. 相似文献
12.
The reactions of Fe(CO)5 or Fe3(CO)12 with NaBEt3H or KB[CH(CH3)C2H5]3H, respectively and treatment of the resulting carbonylates M2Fe(CO)4, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M2[Fe2(CO)6(μ‐Se)2]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)2+, cp = η5‐C5H5 afforded the selenolato complexes [Fe2(CO)6(μ‐SeR)2], R = CH2SiMe3 ( 1 ), CH2Ph ( 2 ), p‐CH2C6H4NO2 ( 3 ), o‐CH2C6H4CH2 ( 4 ) and cpFe(CO)2+ ( 5 ) in moderate to good yields. A similar reaction employing Ru3(CO)12, Se and p‐O2NC6H4CH2Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1 , 3 , 4 and 5 were determined and revealed butterfly structures of the Fe2Se2 cores. The substituents in 1 , 3 and 5 adopt different conformations depending on their steric demand. In 4 , the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The 77Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes. 相似文献
13.
Katharine F. Bowes Christopher Glidewell John N. Low Manuel Melguizo Antonio Quesada 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(1):o4-o8
Crystallization of 2‐amino‐4‐chloro‐6‐morpholinopyrimidine, C8H11ClN4O, (I), yields two polymorphs, both with space group P21/c, having Z′ = 1 (from diethyl ether solution) and Z′ = 2 (from dichloromethane solution), denoted (Ia) and (Ib), respectively. In polymorph (Ia), the molecules are linked by an N—H⋯O and an N—H⋯N hydrogen bond into sheets built from alternating R(8) and R(40) rings. In polymorph (Ib), one molecule acts as a triple acceptor of hydrogen bonds and the other acts as a single acceptor; one N—H⋯O and three N—H⋯N hydrogen bonds link the molecules in a complex chain containing two types of R(8) and one type of R(18) ring. 2‐Amino‐4‐chloro‐6‐piperidinopyrimidine, C9H13ClN4, (II), which is isomorphous with polymorph (Ib), also has Z′ = 2 in P21/c, and the molecules are linked by three N—H⋯N hydrogen bonds into a centrosymmetric four‐molecule aggregate containing three R(8) rings. 相似文献
14.
Doyle Britton 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(1):o14-o16
The structures of o‐chlorobenzonitrile, C7H4ClN, (I), and o‐bromobenzonitrile, C7H4BrN, (II), have similar packing arrangements, even though Z′ = 4 in (I) and Z′ = 1 in (II). Both structures involve X⋯N interactions, as well as weak C—H⋯X and C—H⋯N hydrogen bonds. The four crystallographically independent molecules in (I) are related by pseudosymmetry. 相似文献
15.
Judith C. Gallucci Rajendrakumar Reddy Gadikota Todd L. Lowary 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):e365-e365
The crystal structure of the title compound, C20H17NO4S, (I), was determined in order to compare the solution and solid‐state conformations. The molecule was synthesized as a building block for incorporation into oligosaccharides comprised of conformationally restricted furanose residues. The furanose ring adopts an envelope conformation with the ring O atom displaced above the plane (an OE conformation). The pseudorotational phase angle (P) is 88.6° and the puckering amplitude (τm) is 31.5°. The C2—C1—S—C(Ph) torsion angle is ?163.2 (2)°, which places the aglycone in the exo‐anomeric effect preferred position. The C1—S—C14 bond angle is 99.02 (13)° and the plane of the cresyl moiety is oriented nearly parallel to the four in‐plane atoms of the furanose ring envelope. The orientation about the C4—C5 bond is gauche–gauche [Bock & Duus (1994). J. Carbohydr. Chem. 13 , 513–543]. 相似文献
16.
Alejandro J. Metta‐Magaña Marcela Lopez‐Cardoso Gabriela Vargas Prof. Dr. Keith H. Pannell 《无机化学与普通化学杂志》2012,638(11):1677-1682
The synthesis and characterization of selenium‐containing stannanes, (o‐MeSeC6H4CH2)Sn(Ph)3–nCln [n = 0 ( 1Se ); 1 ( 2Se ); 2 ( 3Se )], is presented. The increasing Lewis acidity at tin in the series 1Se → 2Se → 3Se is reflected in their respective solid state arrangements and supramolecular architecture by interactions of the type Se ··· Se, Sn ··· Se, and Cl ··· H–C. Overall the capacity of the selenium atom to form bidentate interactions creates geometric assemblies distinctly different to those of the oxygen and sulfur analogs. 相似文献
17.
Masashi Shiotsuki Atsushi Nakagawa Jesus Rodriguez Castañon Naoya Onishi Tatsurou Kobayashi Fumio Sanda Toshio Masuda 《Journal of polymer science. Part A, Polymer chemistry》2010,48(23):5549-5556
End‐functionalized poly(phenylacetylene)s were synthesized by the polymerization of phenylacetylene (PA) using the well‐defined palladium catalysts represented as [(dppf)PdBr(R)] {dppf = 1,1′‐bis(diphenylphosphino)ferrocene}. The Pd catalysts having a series of R groups such as o‐tolyl, mesityl, C(Ph)?CPh2, C6H4‐o‐CH2OH, C6H4‐p‐CN, and C6H4‐p‐NO2 in conjunction with silver triflate polymerized PA to give end‐functionalized poly(PA)s bearing the corresponding R groups in high yields. The results of IR and NMR spectroscopies and MALDI‐TOF mass analyses proved the introduction of these R groups at one end of each polymer chain. The poly(PA) bearing a hydroxy end group was applied as a macroinitiator to the synthesis of a block copolymer composed of poly(PA) and poly(β‐propiolactone) moieties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
18.
The o‐substituted hybrid phenylphosphines, PPh2(o‐C6H4NH2) and PPh2(o‐C6H4OH), could be deprotonated with LDA or n‐BuLi to yield PPh2(o‐C6H4NHLi) and PPh2(o‐C6H4OLi), respectively. When added to a solution of (η5‐C5H5)Fe(CO)2I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η5‐C5H5)Fe(CO)[C(O)NH(o‐C6H4)PPh2‐C,P‐η2] for the former and mainly a zwitterionic complex 2 , (η5‐C5H5)Fe+(CO)2[PPh2(o‐C6H4O?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η5‐C5H5)Fe(CO){NH2(o‐C6H4)PPh2‐N,P‐η2}+]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction. 相似文献
19.
Jens Beckmann Dainis Dakternieks Andrew Duthie Edward R. T. Tiekink 《无机化学与普通化学杂志》2002,628(13):2948-2953
The six‐, eight‐ and twelve‐membered cyclo‐siloxanes, cyclo‐[R2SiOSi(Ot‐Bu)2O]2 (R = Me ( 1 ), Ph ( 2 )), cyclo‐(t‐BuO)2Si(OSiR2)2O (R = Me ( 3 ), Ph ( 4 )), cyclo‐R2Si[OSi(Ot‐Bu)2]2O (R = Me ( 5 ), Ph ( 6 )) and cyclo‐[(t‐BuO)2Si(OSiMe2)2O]2 ( 3a ) were synthesized in high yields by the reaction of (t‐BuO)2Si(OH)2 and [(t‐BuO)2SiOH]2O with R2SiCl2 and (R2SiCl)2O (R = Me, Ph). Compounds 1 — 6 were characterized by solution and solid‐state 29Si NMR spectroscopy, electrospray mass spectrometry and osmometric molecular weight determination. The molecular structure of 4 has been determined by single crystal X‐ray diffraction and features a six‐membered cyclo‐siloxane ring that is essentially planar. The reduction of 1 — 6 with i‐Bu2AlH (DIBAL‐H) led to the formation of the metastable aluminosiloxane (t‐BuO)2Si(OAli‐Bu2)2 ( 7 ) along with Me2SiH2 and Ph2SiH2. 相似文献
20.
Nada Kouti‐Hulita Miroslav
egarac 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(3):o171-o173
In the crystal structure of (R)‐N,N‐diisopropyl‐3‐(2‐hydroxy‐5‐methylphenyl)‐3‐phenylpropylaminium (2R,3R)‐hydrogen tartrate, C22H32NO+·C4H5O6−, the hydrogen tartrate anions are linked by O—H⋯O hydrogen bonds to form helical chains built from (9) rings. These chains are linked by the tolterodine molecules via N—H⋯O and O—H⋯O hydrogen bonds to form separate sheets parallel to the (101) plane. 相似文献