Hydrolysis of chlorophosphine ligands on platinum and palladium. 31P and 195Pt nmr studies and the crystal and molecular structures of cis-[PtCl2(PPh2OH)2]•C4H8O and [Pd2(µ-Cl)2{(P(OEt)2O)2H}2]

1985 ◽  
Vol 63 (11) ◽  
pp. 2949-2957 ◽  
Author(s):  
David Eric Berry ◽  
Kathryn Anne Beveridge ◽  
Gordon William Bushnell ◽  
Keith Roger Dixon
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Studies ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Hydrolysis Products ◽  
Hydrolysis Of ◽  
Controlled Hydrolysis

Controlled hydrolysis of cis-[PtCl2(PPh2Cl)2] gives cis-[PtCl2(PPh2OH)2] which crystallizes as a tetrahydrofuran solvate in the monoclinic space group P21/n, with a = 14.647(3), b = 15.089(3), c = 13.107(2) Å, β = 91.22(3)°. This is the first example of a complex containing a cis-M(PR2OH)2 group to be structurally characterized since further reaction to [Formula: see text] ligand systems is the more usual outcome of such hydrolyses. An example of the latter type, [Pd2(μ-Cl)2-{(P(OEt)2O)2H}2], crystallizes in the monoclinic space group P21/c, a = 9.674(2), b = 20.722(5), c = 8.578(2) Å, β = 92.75(3)°. Complete X-ray diffraction studies are reported for both crystals. Synthesis and 31P{1H} and 195Pt{1H} nmr studies are reported for the complexes [PtCl2(PEt3)(PR2Cl)], R = OEt, Ph, Cy, Et, or Bu′, which have cis stereochemistry except when R = Bu′, and for cis-[PtCl2(PR2Cl)2], R = OEt, Ph, or Et, and also for the hydrolysis products, cis-[PtCl2(PEt3)(PR2OH)], R = OEt or Ph, and cis-[PtCl2(PR2OH)2], R = OEt, Ph, or Et. Analogous products for palladium are generally less stable and more difficult to characterize. The complex of products from hydrolysis of palladium/P(OEt)2Cl compounds is discussed in detail.

Hydrolysis and condensation of chlorophosphine and alkyl phosphite ligands on platinum and palladium. 31P and 195Pt nuclear magnetic resonance studies and the crystal and molecular structures of [Pt2Cl4{μ-(EtO)2POP(OEt)2}2] and [Cl2Pt{μ-(P(OEt)2O)2P(O)}PtCl(PEt3)2]

1986 ◽  
Vol 64 (2) ◽  
pp. 343-352 ◽  
Author(s):  
David Eric Berry ◽  
Kathryn Anne Beveridge ◽  
Gordon William Bushnell ◽  
Keith Roger Dixon ◽  
Alan Pidcock
Keyword(s):  
Spin Systems ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Hydrolysis Of ◽  
Related Compounds ◽  
Alkyl Phosphite

Hydrolysis of cis-[PtCl2-{P(OEt)2Cl}2] results in condensation of the phosphite to form [Pt2Cl4{μ-(EtO)2POP(OEt)2}2], which crystallizes in the monoclinic space group P21/n, with a = 13.814(7), b = 11.429(4), c = 10.726(5) Å, β = 106.30(5)°. Reactions of P(OEt)2Cl or (EtO)2POP(OEt)2 with [Pt2Cl4(PEt3)2] also yield very easily hydrolyzed products but in these cases an even more complex condensation occurs to yield [Cl2Pt{(μ-(P(OEt)2O)2P(O)}PtCl(PEt3)2], which crystallizes in the monoclinic space group P21/c, a = 17.547(8), b = 19.775(6), c = 11.268(3) Å, β = 106.42(3)°. Complete X-ray diffraction studies are reported for both crystals, confirming the presence of double (EtO)2POP(OEt)2 bridges in [Pt2Cl4{(μ-(EtO)2POP(OEt)2}2] and a novel triphosphite bridge in [Cl2Pt{μ-(P(OEt)2O)2P(O)}PtCl(PEt3)2]. Detailed analyses and computer simulation of the 31P{1H} and 195Pt{1H} nmr spectra of these complexes are also described, together with studies of the related compounds, [Pt2Me4{μ-(EtO)2POP(OEt)2}2] and [Cl2(Et3P)Pt{μ-(EtO)2POP(OEt)2}PtCl2(PEt3)]. In conjunction with previous studies of [Pt2Cl2(dppm)2] and related complexes, these spectra provide examples of several types of AA′XX′ spin systems and the analysis of these systems is discussed in detail.

Strukturuntersuchungen an Diaryldichalkogeniden: Die Molekülstrukturen von [2,4,6-(CF3)3C6H2S]2,[2,4,6-Me3C6H2Te]2 und [2-Me2N-4,6-(CF3)2C6H2Te]2 / Structural Investigations of Diaryl Dichalcogenides: The Molecular Structures of [2,4,6-(CF3)3C6H2S]2, [2,4,6-Me3C6H2Te]2 and [2-Me2N-4,6-(CF3)2C6H2Te]2

1992 ◽  
Vol 47 (3) ◽  
pp. 305-309 ◽  
Author(s):  
Anja Edelmann ◽  
Sally Brooker ◽  
Norbert Bertel ◽  
Mathias Noltemeyer ◽  
Herbert W. Roesky ◽  
...  
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Structural Investigations ◽  
Space Group ◽  
X Ray

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).

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

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.

Spectroscopic and X-Ray Investigation of Cobalt(III) Complexes with 2-Oximinocarboxylic Acids

1993 ◽  
Vol 48 (4) ◽  
pp. 409-417 ◽  
Author(s):  
Rostislav D. Lampeka ◽  
Zamira D. Uzakbergenova ◽  
Victor V. Skopenko
Keyword(s):  
Electronic Absorption Spectra ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Octahedral Structure ◽  
Space Group ◽  
X Ray ◽  
H Nmr ◽  
Nmr Data ◽  
R Factors

Mixed complexes of Co(III) with 2-oximinopropionic (H2A) or 2-oximino-3-phenylpropionic (H2B) acid and different amine (imidazole, benzimidazole, pyridine, β-picoline, γ-picoline) are reported. Characterization of the complexes was based upon elemental analysis, conductivity and JR, 1H NMR, and electronic absorption spectra, and X-ray diffraction analysis. The organic ligands behave as O,N donors via the carboxyl oxygen and the oxime nitrogen atoms. A trans-octahedral structure has been assigned to the bis(2-oximinocarboxylato)bis(amine)cobalt(III) on the basis of 1H NMR data.The crystal and molecular structures of the complexes trans-[bis(2-oximinopropionato)bis-(imidazole)]- (I) and trans-[bis(2-oximinopropionato)bis(pyridine)]cobalt(III) (II) were determined. I crystallizes in space group P2/n with a = 14.1 67(2), b = 8.774(1), c = 14.785(2) Å,β = 113.37(1)°, Z = 4, Dcalc = 1.568 g · cm-3. II crystallizes in space group P1̄ with a = 9.122(2), b = 10.038(2), c = 11.759(2) Å, α = 69.95(1)°, β = 67.47(2)°, γ = 69.49(2)°, Ζ = 2, Dcalc = 1.547 g cm-3. The structures were refined to unweighted R factors of 0.036 and 0.028, respectively. The coordination sphere around Co is pseudo-octahedral with the 2-oximinopropionato ligands occupying four equatorial positions, and the amines in axial positions.

Crystal structures of 1-(m-nitrophenyl)-2,2-dicarboethoxy-3-phenyl-pyrrolidin-5-one (C22H22N2O7) (I) and 1-(p-chlorophenyl)-2,2-dicarboethoxy-3-phenyl-pyrrolidin-5-one (C22H22NO5Cl) (II)

1989 ◽  
Vol 189 (3-4) ◽  
Author(s):  
G. D. Nigam ◽  
G. Mattern ◽  
R. Fröhlich
Keyword(s):  
Crystal Structures ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures

AbstractThe crystal and molecular structures of 1-(m-nitrophenyl)-2,2-dicarboethoxy-3-phenyl-pyrrolidin-5-one (I) and 1-(p-chlorophenyl)-2,2-dicarboethoxy-3-phenyl-pyrrolidin-5-one (II) have been determined by X-ray diffraction methods. (I) crystallizes in the monoclinic space group

Two crystal structures of 10,10′-(l,4-phenylene-dimethylidene)-bis-9,10-H-anthracenone

1992 ◽  
Vol 200 (3-4) ◽  
Author(s):  
G. Dewald ◽  
M. Hanack ◽  
E.-M. Peters ◽  
L. Walz
Keyword(s):  
Crystal Structures ◽  
Diffraction Data ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hydrogen Atoms ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures

AbstractThe crystal and molecular structures of dimorphic 10,10′-(1,4-phenylene-dimethylidene)-bis-9,10-H-anthracenone (1) have been determined using X-ray diffraction data. The compound crystallizes either in the monoclinic space groupSince all non-hydrogen atoms are of pure

Addition der schweren Chalkogen-Atome und Halogenonium-Ionen an Carbodiphosphorane / Addition of the Heavy Chalkogen Atoms and Halogenonium Ions to Carbodiphosphoranes

1985 ◽  
Vol 40 (10) ◽  
pp. 1293-1300 ◽  
Author(s):  
H. Schmidbaur ◽  
Chr. Zybill ◽  
D. Neugebauer ◽  
G. Müller
Keyword(s):  
Room Temperature ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Molar Ratios ◽  
Structure Factors ◽  
Elemental Iodine

Hexaphenylcarbodiphosphorane Ph3P=C=PPh3 (1) forms deeply coloured, crystalline 1:1 ad- ducts with elemental sulfur, selenium and tellurium (2, 3 and 7, respectively). A superior method of synthesis for 7 is the reaction of Na2Te with (Ph3P)2CCl⊕Cl⊖. All three compounds are thermally unstable and decompose at or below room temperature. A selenium adduct 5 was also obtained with Me3P = C = PPh, (4). The compounds 2 and 3 can be alkylated at the chalkogen atoms using MeOSO2F or PhCH2Cl. Oxydation of 3 leads to Se - Se coupling.Addition of elemental iodine to 1 in molar ratios 1:1. 2:3 and 1:2 affords salt-like products composed of the (Ph2P)2Cl⊕ cation associated with I⊖ and/or I3⊖ anions (8a-c).The crystal and molecular structures of 3 and 8b have been determined by single crystal X-ray diffraction. 3′, containing one half equivalent of disordered tetrahydrofuran, crystallizes in the monoclinic space group P21/n (a = 10.848(6), b = 17.433(8). c = 16.848(9) Å, β = 91.51(5)°. V = 3185.07 Å3, ϱx = 1359 gcm-3, Z = 4). Based on 3488 structure factors, the final R value was 0.103. The selenium is attached to the ylidic carbon atom without major changes of the Ph3P=C=PPh3 skeleton (C - Se = 1.99 Å). 8b crystallizes in the triclinic space group P1̄ (a = 9.935(2). b = 11.507(2), c = 16.646(3) Å, α = 90.91(1), β = 112.00(1), γ = 96.60(1)°, V = 1749.15 A3, ϱx = 1.741 gcm-3, Z = 2). Refinement of 382 parameters on 5096 structure factors converged at R = 0.043. The molecular structure shows close similarities to the selenium adduct 3 (C-I = 2.12 Å).

Synthesis and characterization of [MII(bqb)] (M = Co, Ni, Cu), [N(n-Bu)4][CoIII(bqb)(CN)2], and [N(n-Bu)4][CoIII(bqb)(N3)2] containing deprotonated N,N'-bis(2-quinolinecarboxamide)-1,2-benzene (bqb) – X-ray crystal structures of [NiII(bqb)] and [N(n-Bu)4][CoIII(bqb)(N3)2]

2006 ◽  
Vol 84 (7) ◽  
pp. 971-978 ◽  
Author(s):  
Soria Meghdadi ◽  
Mehdi Amirnasr ◽  
Vratislav Langer ◽  
Alison Zamanpoor
Keyword(s):  
Crystal Structures ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Elemental Analyses

Cobalt(II), nickel(II), copper(II), and two cobalt(III) complexes of a new dianionic ligand, bqb, [H2bqb = N,N'-bis(2-quinolinecarboxamide)-1,2-benzene] have been synthesized and characterized by elemental analyses, IR, and 1H NMR spectroscopy. The crystal and molecular structures of the [Ni(bqb)] (2) and [N(n-Bu)4][CoIII(bqb)(N3)2] (5) complexes were determined by X-ray crystallography. Complex 2 crystallizes in the monoclinic space group C2/c with a distorted square-planar structure including two short Ni–N (1.848 Å) and two long Ni–N (1.958 Å) bonds. The structure consists of sheets formed in the plane parallel to the b axis and diagonal to vectors a and c by intermolecular hydrogen bonds. Complex 5 crystallizes in the monoclinic space group C2 with a distorted octahedral structure. The [N(n-Bu)4]+ ion is disordered at the C3A and C4A atoms of one Bu. The IR and 1H NMR spectra of the complexes are also discussed.Key words: N4-dianionic amido ligand (bqb), (bqb) complexes of Co(II), Ni(II), Cu(II), and Co(III), azide, cyanide, X-ray crystal structures.

Metal complexes of dicamba: the crystal and molecular structures of dicamba(3,6-Dichloro-2-methoxybenzoic acid) and catena-μ-Aqua-diaquabis(3,6-dichloro-2-methoxybenzoato)zinc(II) dihydrate

1983 ◽  
Vol 36 (11) ◽  
pp. 2175 ◽  
Author(s):  
G Smith ◽  
EJ O'Reilly ◽  
CHL Kennard
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bridging Ligand ◽  
Methoxy Groups ◽  
A Cell ◽  
Methoxybenzoic Acid

The crystal structures of the herbicide, dicamba (3,6-dichloro-2-methoxybenzoic acid) and the zinc(II) complex of this acid, {[Zn(dicamba)2(H2O)3].2H2O}}n (1), have been determined from X-ray diffraction data and refined by least squares to final residuals of 0.034 and 0.043 respectively. Dicamba is triclinic, space group P1, Z 2 with a cell a 7.232(1), b 7.971(1), c 9.050(3) �, α 102.76(3), β 91.33(3), γ 110.38(1)�, while (1) is monoclinic, space group P21/n, Z 4 with a cell a 10.467(1), b 8.135(3), c 28.079(2) �, β 96.497(7)�. Dicamba forms hydrogen-bonded cyclic dimers [O---O, 2.655(7) �] with the carboxyl and the methoxy groups synclinal to the benzene ring. The dicamba ligands retain their conformation in the ZnII complex and are cis-related and unidentate [Zn-0,2.083,2.095(4) �]. Three of the waters are coordinated [Zn-0, 2.036, 2.055, 2.099(4) �] with one of these also acting as a bridging ligand between the octahedral zinc centres [Zn-0, 2.326(4) �], giving a 'linear' polymer structure [Zn-0-Zn bridge angle, 133.6(3)�]. The MnII and CoII complexes of dicamba [(2) and (3)] have been confirmed as isomorphous and isostructural with the ZnII analogue.

Crystal and Molecular Structures of the Functional Lithium Cyclopentadienides [Li(tmeda)][R2PCMe2C5H4], R = Ph, Me

2000 ◽  
Vol 55 (11) ◽  
pp. 1005-1010 ◽  
Author(s):  
Ulrich Jürgen Bildmann ◽  
Martin Winkler ◽  
Gerhard Müller Fachbereich
Keyword(s):  
Solid State ◽  
Functional Group ◽  
Molecular Structures ◽  
The Other ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray ◽  
Crystal And Molecular Structures

The crystal and molecular structures of the phosphinomethyl-substituted lithium cyclopentadienides [Li(tmeda)][R2PCMe2C5H4], R = Ph (1), Me (2) (tmeda = N,N,N',N'-tetramethylethylenediamine) were determined as their tmeda adducts on the basis of low temperature single crystal X-ray diffraction. (Crystal data: 1: monoclinic, space group P21/n, a = 8.511(5), b = 11.936(2), c = 24.20(1) Å, β = 90.02(3)°, Z = 4.2: monoclinic, space group P21/n, a = 10.887(2), b = 13.326(2), c = 13.131(2) Å, β= 92.872(6)°, Z = 4). In both compounds lithium has a slightly distorted 17 coordination to the cyclopentadienide (Cp) ring. There are no interactions between lithium and the phosphine donors in the solid state as the phosphinomethyl substituents are oriented to the other side of the Cp ring for steric reasons. The isopropene-substituted lithium cyclopentadienide, which is formed as a by-product in the synthesis of phosphinomethyl cyclopentadienides containing a CMe2 bridge, was also structurally characterized as its tmeda adduct [Li(tmeda)][H2C=CMeC5H4] (3). (Crystal data: monoclinic, P21/c, a = 8.00(2), b = 16.701(2), c = 11.942(6) Å, β= 112.68(7)°, Z = 4). As in 1 and 2, lithium is η5 -coordinated to the Cp ring, and there is no interaction of the functional group (isopropene) with lithium.

Sign in / Sign up

Export Citation Format

Share Document