scholarly journals Structural studies of steric effects in phosphine complexes. Part XI. Synthesis, characterization, crystal and molecular structure of the dinitrato(trimesitylarsine)mercury(II) dimer

1983 ◽  
Vol 61 (2) ◽  
pp. 257-262 ◽  
Author(s):  
Elmer C. Alyea ◽  
Shelton A. Dias ◽  
George Ferguson ◽  
Pik Y. Siew
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Cone Angle ◽  
Mean Value ◽  
Monoclinic Space Group ◽  
Structural Studies ◽  
Torsion Angles ◽  
H Nmr ◽  
Phosphine Complexes ◽  
Nmr Data

The synthesis and crystal and molecular structure of the dinitrato(trimesitylarsine)mercury(II) dimer are reported. The compound [HgAs(mesityl)3(NO3)2]2 belongs to the monoclinic space group P21/c[Formula: see text] with a = 20.001(2), b = 17.591(5), c = 16.553(2), β = 99.991(6), and Z = 4; the asymmetric unit contains two independent half dimers. The structure was refined to a final R of 0.0458 for 2631 observed reflections measured by diffractometer with 2 < θ < 20°. The crystal structure consists of discrete centrosymmetric dimeric molecules of [HgAs(mesityl)3(NO3)2]2 separated by normal van der Waals distances. The mercury coordination in both dimers I and II is characterized by three strong, nearly coplanar bonds (in I Hg—As 2.476(3), Hg—O 2.41(2) and 2.20(2), and in II Hg—As 2.482(3), Hg—O 2.28(2) and 2.39(2), and three weaker Hg—O bonds in the range 2.55–2.90 Å. Both independent trimesitylarsine ligands have the same regular propeller conformation (Hg—As—C—C torsion angles of 45 to 50°) and the largest C—As—C angles (mean value 112.5(8)°) yet determined. The As(mesityl)3 cone angle is 202°. The two independent dimers differ primarily in the orientation of the non-bridging nitrato groups. Nitrato vibrational and arsine 1H nmr data are also presented for [HgAs(mesityl)3(NO3)2]2, which becomes monomeric in dichloroethane solution.

Structural studies of steric effects in phosphine complexes. Part VII. Synthesis, crystal and molecular structure of the chloroperchloratotri(o-tolyl)phosphinemercury(II) dimer

1979 ◽  
Vol 57 (17) ◽  
pp. 2217-2222 ◽  
Author(s):  
Elmer C. Alyea ◽  
Shelton Dias ◽  
George Ferguson ◽  
Masood Khan
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Cone Angle ◽  
Mercury Atom ◽  
Intramolecular Interactions ◽  
Coordination Geometry ◽  
Structural Studies ◽  
Orthorhombic Space Group ◽  
Phosphine Complexes ◽  
Trigonal Bipyramidal

The synthesis and crystal and molecular structure of the chloroperchloratotri(o-tolyl)phosphinemercury(II) dimer are reported. The compound [HgP(o-tolyl)3ClClO4]2 belongs to the orthorhombic space group Pbca [Formula: see text] with a = 12.218(2), b = 13.814(2), c = 26.074(3) Å, and Z = 4. The structure was refined to a final R of 0.046 for 2584 reflections measured by diffractometer. The crystal structure consists of discrete centrosymmetric dimeric molecules of [HgP(o-tolyl)3ClClO4]2 separated by normal van der Waals distances. The unique mercury atom forms two strong bonds (Hg—P 2.395(3), Hg—Cl(1) 2.332(4) Å) which deviate from linearity (P—Hg—Cl 164.1(1)°) and two weak bonds (Hg—O(1) 2.73(2) to the perchlorato group, Hg—Cl(1 *) 3.109(4) Å linking the mercury atoms about centers of symmetry). The four-fold coordination geometry about each mercury can be described as trigonal bipyramidal with the phosphorus and Cl(1) axial, and one equatorial site unoccupied. Intramolecular interactions are discussed with the assistance of cone angle calculations and a ligand profile for P(o-tolyl)3 (θ = 198°). Vibrational and 31P nmr spectra data are also presented for [HgP(o-tolyl)3ClClO4]2.

Structural studies of steric effects in phosphine complexes. Synthesis and crystal and molecular structure of the dinitrato(tricyclohexylphosphine)mercury(II) dimer

1977 ◽  
Vol 16 (9) ◽  
pp. 2329-2334 ◽  
Author(s):  
Elmer C. Alyea ◽  
Shelton A. Dias ◽  
George. Ferguson ◽  
Roderic J. Restivo
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Steric Effects ◽  
Structural Studies ◽  
Phosphine Complexes

Reactions of Ni(NO)I with pyrazolyl gallate ligands: crystal and molecular structure of [Me2Ga(N2C5H7)(OCH2CH 2NMe2)]Ni(NO)

1979 ◽  
Vol 57 (23) ◽  
pp. 3107-3112 ◽  
Author(s):  
Kenneth S. Chong ◽  
Steven J. Rettig ◽  
Alan Storr ◽  
James Trotter
Keyword(s):  
Molecular Structure ◽  
Room Temperature ◽  
Crystal And Molecular Structure ◽  
Nickel Atom ◽  
Reaction Sequence ◽  
Full Matrix ◽  
Linear Fashion ◽  
Bond Lengths ◽  
H Nmr ◽  
Nmr Data

Ni(NO)I reacts readily with pyrazolyl gallate ligands Na+L− (where L = MeGa(N2C3H3)3, MeGa(N2C5H7)3, and [Me2Ga(N2C5H7)(OCH2CH2NMe2)]) to yield four-coordinate nickel nitrosyl complexes, LNi(NO). In addition, the compound [Me2Ga(N2-C5H7)(OCH2CH2 NMe2)]Ni(N2C5H7)2Ni(NO) has been isolated from one reaction sequence. 1H nmr data show [Me2Ga(N2C5H7)(OCH2CH2NMe2)]Ni(NO) to be stereochemically non-rigid at room temperature in solution. Crystals of [dimethyl(N,N-dimethylethanol-amino)(3,5-dimethylpyrazolyl)gallato(N(2),N(3),O)] nitrosylnickel(I) are monoclinic, a = 9.119(1), b = 13.900(2), c = 14.284(2) Å, β = 107.96(1)°, Z = 4, space group P21/c. The structure was solved by Patterson and Fourier syntheses and was refined by full-matrix leastsquares procedures to R = 0.025 and Rw = 0.032 for 1828 reflections with I ≥ 3σ(I). The coordination about the nickel atom is severely distorted tetrahedral with angles at nickel ranging from 84.4(1) to 133.5(1)°. The nitrosyl group is coordinated in a non-linear fashion with Ni—N—O = 162.3(4)°, Ni—N = 1.632(4) and N—O = 1.147(4) Å. Other important bond lengths (corrected for libration) are: Ni—O, 2.045(2), Ni—N(pyrazolyl), 1.989(3), Ni—N(amino), 2.071(3), Ga—O, 1.922(2), Ga—N, 1.998(3), and Ga—C, two at 1.971(6) Å.

Sign in / Sign up

Export Citation Format

Share Document