Synthesis, spectroscopic characterization, and structural studies of new Cu(I) and Cu(II) complexes containing organophosphorus ligands, and crystal structures of (Ph3P)2Cu[S2PMe2], (Ph3P)2Cu[(OPPh2)2N], Cu[(OPPh2)2N]2, and Cu[(OPPh2)(SPPh2)N]2

2001 ◽  
Vol 79 (5-6) ◽  
pp. 983-991 ◽  
Author(s):  
Anca Silvestru ◽  
Adina Rotar ◽  
John E Drake ◽  
Michael B Hursthouse ◽  
Mark E Light ◽  
...  

The Cu(I) complexes, (Ph3P)2CuL (L = [S2PMe2]-, [OSPR2]- (R = Me, Ph), [(XPR2)(YPR'2)N]- (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph; O, S, OEt, Ph; S, S, Me, Me)) and Cu(II) complexes, CuL2 (L = [(XPR2)(YPR'2)N]- (X, Y, R, R' = O, O, Ph, Ph; O, S, Ph, Ph)), have been prepared. The Cu(I) derivatives were characterized by multinuclear NMR spectroscopy and in two cases by X-ray crystallography. (Ph3P)2Cu[S2PMe2] (1) crystallizes in the orthorhombic space group P212121 (No. 19) with cell parameters a = 9.782(2), b = 17.808(4), c = 20.216(4) Å, V = 3521(6) Å3 and Z = 4, and (Ph3P)2Cu[(OPPh2)2N] (4) in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 9.8079(2), b = 12.9141(3), c = 22.5666(5) Å, α = 75.714(2), β = 79.465(2), γ = 68.2770(8)°, V = 2559.9(1) Å3 and Z = 2. In both cases the phosphorus ligands are bidentate, thus resulting in monomeric molecules that contain tetrahedral CuP2S2 and CuP2O2 cores. The molecular structures of two of the Cu(II) derivatives were also determined. Cu[(OPPh2)2N]2 (8) and Cu[(OPPh2)(SPPh2)N]2 (9) crystallize in the triclinic space group P[Formula: see text] (No. 2) with cell parameters a = 8.887(2), b = 10.739(2), c = 12.477(3) Å, α = 77.61(3), β = 76.15(5), γ = 79.46(3)°, V = 1118.3(4) Å3 and Z = 1 for 8, and a = 9.626(2), b = 14.151(3), c = 24.752(5) Å, α = 88.23(3), β = 79.93(3), γ = 89.77(3)°, V = 3181(1) Å3 and Z = 3 for 9. The molecule of Cu[(OPPh2)2N]2 (8) has a planar CuO4 core, while in Cu[(OPPh2)(SPPh2)N]2 (9) both planar and tetrahedral copper cores are observed in a ratio of 1:2.Key words: structure, copper, thiophosphinates, oxo- and thio-imidodiphosphinates

2007 ◽  
Vol 62 (10) ◽  
pp. 1271-1276 ◽  
Author(s):  
Liang Chen ◽  
Xian-Wen Wanga ◽  
Jing-Zhong Chen ◽  
Jian-Hong Liu

The complexes Mn(Cl3CCOO)2(4,4′-bpy) (1) and [Cu2(ClCH2COO)(2,2′-bpy)2(OH)(H2O)]-(NO3)2(2) (bpy = bipyridine) were generated under mild reaction conditions and characterized by IR spectra, thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), and single crystal X-ray diffraction. Compound 1 exhibits a two-dimensional network with octahedrally coordinated Mn(II) atoms linked by 4,4′-bpy ligands and Cl3COO− ligands. Compound 2 features a supramolecular structure of binuclear complexes, with edge-sharing five-coordinated square-pyramidal units bridged by the ClCH2COO− ligand, an OH− group and a water molecule. Complex 1 crystallizes in the orthorhombic space group Pbcn with cell parameters: a = 16.5390(17), b = 11.6396(17), c = 9.9181(12) Å, V = 1909.3(4) Å3, Z = 4, wR2 = 0.1576. Complex 2 crystallizes in the triclinic space group P1̅ with cell parameters: a = 7.6190(15), b = 11.151(2), c = 16.640(3) Å , α = 73.13(3), β = 80.89(3), γ = 74.51(3)°, V = 1298.73(4) Å3, Z = 2, wR2 = 0.1265.


2009 ◽  
Vol 64 (5) ◽  
pp. 565-569 ◽  
Author(s):  
Saied Ghadimi ◽  
Mehrdad Pourayoubi ◽  
Ali Asghar Ebrahimi Valmoozi

Mixed diamidophosphoric acid esters [(CH3)2N][p-H3C-C6H4-O]P(O)X, where X = NH(CH3) (1), NHCH(CH3)2 (2), NHC(CH3)3 (3) and p-H3C-C6H4-NH (4) were synthesized and characterized by 31P, 31P{1H}, 13C, 1H NMR, and IR spectroscopy and mass spectrometry, and single crystal X-ray diffraction analysis for the compounds 3 and 4. Compound 3 crystallizes in the monoclinic, space group P21/c with unit cell parameters a = 9.006(3), b = 16.286(5), c = 10.319(3) A° , β = 99.633(6)◦, V = 1492.2(8) °A3, Z = 4. The final R value is 0.0622 for 2074 reflections [I ≥ 2σ (I)]. Compound 4 crystallizes in the orthorhombic, space group Pna21 with unit cell parameters a = 7.0459(14), b = 20.934(4), c = 10.436(2) ° A, V = 1539.3(5) °A3, Z = 4. The final R value is 0.0530 for 3025 reflections [I ≥ 2σ (I)].


2020 ◽  
Vol 76 (9) ◽  
pp. 921-926
Author(s):  
Jetnipat Songkerdthong ◽  
Phimphaka Harding ◽  
David J. Harding

Two conformational polymorphs of (N,N-dibutyldithiocarbamato-κ2 S,S′)[tris(3,5-diphenylpyrazol-1-yl-κN 2)hydroborato]cobalt(II), [Co(C45H34BN6)(C9H18NS2)] or [TpPh2Co(S2CNBu2)], 1, are accessible by recrystallization from dichloromethane–methanol to give orthorhombic polymorph 1a, while slow evaporation from acetonitrile produces triclinic polymorph 1b. The two polymorphs have been characterized by IR spectroscopy and single-crystal X-ray crystallography at 150 K. Polymorphs 1a and 1b crystallize in the orthorhombic space group Pbca and the triclinic space group P-1, respectively. The polymorphs have a trans (1a) and cis (1b) orientation of the butyl groups with respect to the S2CN plane of the dithiocarbamate ligand, which results in an intermediate five-coordinate geometry for 1a and a square-pyramidal geometry for 1b. Hirshfeld surface analysis reveals minor differences between the two polymorphs, with 1a exhibiting stronger C—H...S interactions and 1b favouring C—H...π interactions.


2001 ◽  
Vol 79 (5-6) ◽  
pp. 655-669 ◽  
Author(s):  
Martin A Bennett ◽  
Thomas R Mitchell ◽  
Mark R Stevens ◽  
Anthony C Willis

The mono(acetylacetonato) complexes [MCl(O,O'-acac)(η6-arene)] (M = Ru, Os, arene = C6H6, 1,3,5-C6H3Me3, C6Me6; M = Os, arene = 1,2-C6H4Me2, 1,2,3-C6H3Me3), which are formed from [MCl2(η6-arene)]2 and thallium or sodium acetylacetonate, react with thallium acetylacetonate to give bis(acetylacetonato) complexes [M(O,O'-acac)(η1-acac)(η6-arene)]. The η1-acac ligand is bound through the gamma-carbon atom for M = Ru, Os, arene = C6H6; M = Os, arene = 1,2-C6H4Me2, 1,2,3-C6H3Me3 and through a keto-oxygen atom for M = Ru, Os, arene = 1,3,5-C6H3Me3, C6Me6, the difference being attributed to a combination of steric and electronic effects. Cationic ruthenium(II) derivatives [Ru(L)(O,O'-acac)(η6-arene]+ (arene = C6H6, 1,3,5-C6H3Me3, C6Me6; L = DMSO, MeCN, py, PPh3) and [Ru(CO)(O,O'-acac)(η6-arene]+ (arene = 1,3,5-C6H3Me3,C6Me6), and neutral osmium(II) η1-acetato derivatives [Os(η1-OAc)(O,O'-acac)(η6-arene)] (arene = C6H6, 1,2-C6H4Me2, 1,2,3-C6H3Me3, 1,3,5-C6H3Me3, C6Me6) are also described. The molecular structures of the following complexes have been determined by X-ray crystallography: [Os(O,O'-acac)(η1-C-acac)(η6-1,2-C6H4Me2)], triclinic, space group P[Formula: see text] (No. 2), a = 9.922(2), b = 9.974(2), and c = 11.001(2) Å, α = 68.33(1), β = 64.18(1), and γ = 62.38(1)°, V = 849.0(3) Å3, Z = 2; [Os(O,O'-acac)(η1-O-acac)(η6-1,3,5-C6H3Me3)], monoclinic, space group C2/c (No. 15), a = 16.032(4), b = 11.989(3), and c = 21.562(7) Å, β= 108.91(2)°, V = 3921(2) Å, Z = 8; [Os(η1-OAc)(O,O'-acac)(η6-C6H6)], triclinic, space group P[Formula: see text] (No. 2), a = 8.368(4), b = 8.402(4), and c = 11.008(4) Å, α = 71.68(3), β = 69.35(3), and γ = 69.77(3)°, V = 663.0(6) Å3, Z = 2.Key words: arene-ruthenium, arene-osmium, acetylacetone, crystal structures.


1995 ◽  
Vol 50 (7) ◽  
pp. 1018-1024 ◽  
Author(s):  
Axel Michalides ◽  
Dagmar Henschel ◽  
Armand Blaschette ◽  
Peter G. Jones

In a systematic search for supramolecular complexes involving all combinations of the cyclic polyethers 12-crown-4 (12C4), 15-crown-5 (15C 5), 18-crown-6 (18C 6) and dibenzo- 18-crown-6 (DB -18C6), and the geminal di- or trisulfones H2C(SO 2Me)2, H2C (SO2Et)2 and HC (SO2Me)3-n (SO2Et)n (n = 0 -3 ) , only the following four complexes could be isolated and unequivocally characterized by elemental analysis and 1H NMR spectroscopy: [(12C4){H2C (SO2Et)2}2] (3), [(18C6){H2C (S O2Me)2}] (4), [(DB -18C 6){H2C (SO2Et)2}] (5) and [(D B -18C 6)2{HC (SO2Me )(SO2Et)2}3] (6). The structure of 3 (triclinic, space group P1̄) consists of crystallographically centrosymmetric formula units, in which the disulfone molecules are bonded on each side of the ring by two C -H ··· O(crown) interactions originating from the central methylene group (H···O 213 pm) and from the methylene group of one EtSO2 moiety ( H ··· O 237 pm). Formula units related by translation are connected into parallel strands by a third type of reciprocal C -H ···O bond (H ···O 232 pm) between the second H atom of the central methylene group and a sulfonyl oxygen atom of the adjacent unit. The structure of 4 (monoclinic, space group C2/c) showed severe disorder of the crown ether and could not be refined satisfactorily. Compounds 5 and 6 crystallized as long and extremely thin fibres, indicative of linear-polymeric supramolecular structures; single crystals for X-ray crystallography were not available.


1992 ◽  
Vol 47 (3) ◽  
pp. 305-309 ◽  
Author(s):  
Anja Edelmann ◽  
Sally Brooker ◽  
Norbert Bertel ◽  
Mathias Noltemeyer ◽  
Herbert W. Roesky ◽  
...  

Abstract The Molecular Structures of [2,4,6-(CF3)3C6H2S]2 (1) [2,4,6-Me3C6H2Te]2 and [2-Me2N-4,6-(CF3)2C6H2Te]2 (3) have been determined by X-ray diffraction. Crystal data: 1: orthorhombic, space group P212121, Z = 4, a = 822.3(2), b = 1029.2(2), c = 2526.6(5) pm (2343 observed independent reflexions, R = 0.042); 2: orthorhombic, space group Iba 2, Z = 8, a = 1546.5(2), b = 1578.4(2), c = 1483.9(1) pm (2051 observed independent reflexions, R = 0.030); 3: monoclinic, space group P 21/c, Z = 4, a = 1118.7(1), b = 1536.5(2), c = 1492.6(2) pm, β = 98.97(1)° (3033 observed independent reflexions, R = 0.025).


1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.


1984 ◽  
Vol 37 (6) ◽  
pp. 1171 ◽  
Author(s):  
DG Allen ◽  
CL Raston ◽  
BW Skelton ◽  
AH White ◽  
SB Wild

The (�)-benzyl(methyl)(4-methylphenyl)(naphthalen-1-yl)arsonium cation has been synthesized and subsequently resolved by fractional crystallization of monohydrogen [R-(R*,R*)]-2,3-bis(benzoyloxy)- butanedioate salts. The separated diastereoisomers were converted into the corresponding optically active arsonium bromides by ion-exchange column chromatography. The absolute configuration of the arsonium cation exhibiting a positive rotation at 589 nm (sodium D line) has been established as (R) by single-crystal X-ray analysis of both the bromide and hexafluorophosphate salts. The arsonium bromide with [α]D + 54.8�(c, 0.62 in CH2Cl2) crystallizes in the orthorhombic space group P212121 (D24, No.19) with a 22.472(8), b 15.724(7), c 12.585(5) � and U 4447(3) �3. The corresponding hexafluorophosphate with [α]D + 19.3� (c, 0.5 in CH2Cl2) crystallizes in the same space group with a 23.56(2), b 16.40(1), c 13.12(1) � and U 5067(6) � 3. Benzylidene transfer to benzaldehyde from the arsonium ylide derived from either of the arsonium salts produced optically pure (–)-(S)-methyl(4-methylphenyl)(naphthalen-1-yl)arsine, [α]D - 115.9� (c, 0.593 in CHCl3), and partly resolved [R-(R*,R*)]-2,3-diphenyloxiran.


1997 ◽  
Vol 50 (11) ◽  
pp. 1035 ◽  
Author(s):  
Leslie D. Field ◽  
Trevor W. Hambley ◽  
Taian He, ◽  
Anthony F. Masters ◽  
Peter Turner

Decaphenylchromocenium and decaphenylcobaltocenium cations [M(η5-C5Ph5)2]+, M = Cr and Co, were synthesized by oxidation of the corresponding neutral decaphenylchromocene and decaphenylcobaltocene respectively with nitrosyl tetrafluoroborate. The complexes are air-stable and were fully characterized; decaphenylchromocenium tetrafluoroborate (1) and decaphenylcobaltocenium tetrafluoroborate (2) were structurally characterized by X-ray crystallography. Crystals of (1) (as a water/methylene chloride solvate), C70·5H50BClCrF4O0·5, M 1079·42, are triclinic, space group P -1 (No. 2), a 13·634(5), b 17·424(5), c 13·298(4) Å, α 106·45(2), β 101·83(3), γ 74·56(2)°, Z 2. Crystals of (2) (as a water/methylene chloride solvate), C70·5H50BClCoF4O0·5, M 1086·36, are triclinic, space group P-1 (No. 2), a 13·633(2), b 17·683(3), c 13·255(3) Å, α 107·95(1), β 102·71(1), γ 73·23(1)°, Z2.


1996 ◽  
Vol 51 (10) ◽  
pp. 1473-1485 ◽  
Author(s):  
Cornelius G. Kreiter ◽  
Ernst-Christian Koch ◽  
Walter Frank ◽  
Guido J. Reiß

Upon UV irradiation in THF at 208 K tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)- manganese (1) yields solvent stabilized, very reactive dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(tetrahydrofuran)manganese (2), which reacts in situ with one or two molecules of diphenylacetylene (3) and yields four manganese complexes and 1,3-dimethyl-5,6-diphenyl-bicyclo[3.2.1]oct-2-ene-7-one (5), which were separated by HPL chromatography. In addition to tricarbonyl η5-4,6 -dimethyl-1,2-diphenyl-cyclohepta-2,4-dien-1-yl)manganese (4) formed by [5+2]cycloaddition and successive 1,4-H shift, tricarbonyl{ 1′,2′,5′-η-5-methyl-2,3 -diphenyl-5- (2′-methyl-4′,5′-diphenyl-penta-1′,4′-dien-1′,5′-diyl)cyclopent-2-en-1 -one-κ-O}manganese (6) is isolated with a ligand, formed from 2,4-dimethyl-2,4-pentadien-1-yl, two units of 3 and one carbon monoxide. The ligands of tricarbonyl{ 1-4,2′-η-4,6 -dimethyl-1,2-diphenyl-5-(E-1′,2′- diphenyl-vinylen)cyclohepta-1,3-diene}manganese (7), and tricarbonyl{η5-4,6 -dimethyl-1,2-diphenyl-7-(E-1′,2′-diphenyl-vinyl)cyclohepta-2,4-dien-1-yl}m anganese (8) are formed from 2,4-dimethyl-2,4-pentadien-1-yl and of two molecules of 3 each. The crystal and molecular structures of 5 and 6 have been determined by single crystal X-ray diffraction. 5 crystallizes in the triclinic space group P1̅ , a = 992.0(2) pm, b = 996.8(2) pm, c = 1021.0(2) pm, a = 77.67(3)°, β = 61.17(3)°, γ = 88.68(3)°. Complex 6 crystallizes also in the triclinic space group P1̅ ,a = 1023.2(2) pm, b - 1113.8(2) pm, c = 1567.9(3) pm, α = 82.88(3)°, β = 86.93(3)°, 7 = 63.53(3)°. The constitutions of 4, 7 and 8 were elucidated from the IR, NMR and mass spectra. Possible formation mechanisms for the compounds 4-8 are proposed. Complex 7 shows hindered rotations of two phenyl groups with different barriers of energy ΔG≠316 = 68.8 kJ/mol, „ΔH≠ = 67.9 ± 0.7 kJ/mol, ΔS≠ = -2 ± 2 J/mol · K and ΔG≠296 = 60.6 kJ/mol, ΔH≠ = 57.7 ± 1.0 kJ/mol, ΔS≠ = -10 ± 2 J/mol·K due to steric interactions.


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