Abstract:The crystal structure of tetraphenylarsonium nitridotetrachloroosmate(VI), (Ph4As)[OsNC14], has been determined from three-dimensional X-ray diffractometer data. The crystals are tetragonal with unit-cell dimensions a=12.667(3), c=7.820(2) A, space group P4/n and Z=2. Full-matrix least-squares refinement, using 1189 independent reflections, has reached R = 0.037.Two discrete ionic species are present in the structure. The [OsNC14]-anion has 4ram (C4v) point symmetry, and the osmium atom has a square-pyramidal … Show more
“…The As atom lies 0.05 A out of these phenyl-ring planes. The structure of the (AsPh4) + cation is quite similar to those observed in Ph4AsOsNCI4 (Phillips & Skapski, 1975a) and in Ph4AsAuCI 4 (Jones, Guy & Sheldrick, 1975).…”
Section: Description Of the Structure And Discussionsupporting
From a suspension of AsPh4ReO 4 or PPh4ReO 4 in various solutions such as ethanol, methanol, acetone, chloroform, water, benzene, formic acid and others, the red compounds containing oxopentachlororhenate(VI) anions were obtained on reaction with gaseous HCI. AsPh4ReOCI 5 and PPh4ReOC15 crystallize in the space group P4/n, with similar axial lengths. From solutions of these complexes in ethanol the yellow complexes AsPhaReOC14 or PPh4ReOCI 4 could be obtained. The crystal structure of AsPh4ReOCI4 has been determined by single-crystal diffractometry. The structure was solved by the heavy-atom technique and refined by the block-diagonal least-squares method to an R = 0.059 for 1134 reflexions. In the squarepyramidal [ReOCI4I-anion the Re and O atoms lie on a fourfold axis, with Re-O and Re-CI 1.63 (3) and 2-344 (4) A respectively. The AsPh~ cation has 4 ($4) crystallographic symmetry, with As-C 1.91 (1) A and two independent C-As-C angles of 107-2 (5) and 110.6 (5) °. [Crystal data for AsPh4ReOCI4: space group P4/n, a = 13.117 (6), c ---7.358 (4) A.]
“…The As atom lies 0.05 A out of these phenyl-ring planes. The structure of the (AsPh4) + cation is quite similar to those observed in Ph4AsOsNCI4 (Phillips & Skapski, 1975a) and in Ph4AsAuCI 4 (Jones, Guy & Sheldrick, 1975).…”
Section: Description Of the Structure And Discussionsupporting
From a suspension of AsPh4ReO 4 or PPh4ReO 4 in various solutions such as ethanol, methanol, acetone, chloroform, water, benzene, formic acid and others, the red compounds containing oxopentachlororhenate(VI) anions were obtained on reaction with gaseous HCI. AsPh4ReOCI 5 and PPh4ReOC15 crystallize in the space group P4/n, with similar axial lengths. From solutions of these complexes in ethanol the yellow complexes AsPhaReOC14 or PPh4ReOCI 4 could be obtained. The crystal structure of AsPh4ReOCI4 has been determined by single-crystal diffractometry. The structure was solved by the heavy-atom technique and refined by the block-diagonal least-squares method to an R = 0.059 for 1134 reflexions. In the squarepyramidal [ReOCI4I-anion the Re and O atoms lie on a fourfold axis, with Re-O and Re-CI 1.63 (3) and 2-344 (4) A respectively. The AsPh~ cation has 4 ($4) crystallographic symmetry, with As-C 1.91 (1) A and two independent C-As-C angles of 107-2 (5) and 110.6 (5) °. [Crystal data for AsPh4ReOCI4: space group P4/n, a = 13.117 (6), c ---7.358 (4) A.]
“…The geometry of the two coordinated ligands around the metal is distorted with the four nitrogen atoms bent away from the nitrido group. This kind of distortion has been found in other nitridoruthenium(VI) and nitridoosmium(VI) complexes and is ascribed to the repulsion between metal−nitride π-bonding electrons, localized on the metal, and σ-bonding electrons of the ligands. 5c, 2 Perspective view of the [(Ru VI (L) 2 N) 2 (μ-O)] 4+ cation. 3 Molecular orbital diagram of [(Ru VI (L) 2 N) 2 (μ-O)] 4+ .…”
[(n-Bu)4N][RuNCl4]
reacts with 2,5-dimethyl-2,5-hexanediamine (L) in acetone to give a
cationic dimeric RuVI⋮N complex
[(RuVI(L)2N)2(μ-O)]Cl4
(1). The X-ray crystal structure of
1·H2O has been determined. The structure
of 1 shows two Ru⋮N units bridged by a μ-oxo ligand.
The Ru⋮N and Ru−O bond distances are 1.66(1) and
1.9896(8) Å,
respectively.
“…The average N-M-S angles are 107.6 and 107.2°for 1 and 2, respectively; the N-Ru-S angles for 1 are similar to the N-Ru-S angles reported for (N n -Bu 4 )[Ru(N)(NHCOCH 2 CH 2 S) 2 ] (107.1 and 109.7°), and likewise, the N-Os-S angles for 2 are in the range of the N-Os-S angles reported for (N n Bu 4 )[Os(N){O 2 CCH(NHCOCH 3 )CH 2 S} 2 ] and (N n Bu 4 )[Os(N)(O 2 CCH 2 CH 2 S) 2 ] (107.1°-111.9°). 24 N-M-Cl angles are reported to be 104.58°for (AsPh 4 )[Ru(N)Cl 4 )] 25 and 104.29°for (AsPh 4 )[Os(N)Cl 4 )], 26 and the bend of the basal ligands away from the plane of the metal has been attributed to the repulsion between the π-electrons of the metal-nitrogen triple bond and the metal-Cl bonding electrons. 26 The greater bend observed for thiolate-ligated nitrido complexes when compared to the choride-ligated complexes reflects the greater donor ability of the sulfur atom.…”
Section: Resultsmentioning
confidence: 99%
“…24 N-M-Cl angles are reported to be 104.58°for (AsPh 4 )[Ru(N)Cl 4 )] 25 and 104.29°for (AsPh 4 )[Os(N)Cl 4 )], 26 and the bend of the basal ligands away from the plane of the metal has been attributed to the repulsion between the π-electrons of the metal-nitrogen triple bond and the metal-Cl bonding electrons. 26 The greater bend observed for thiolate-ligated nitrido complexes when compared to the choride-ligated complexes reflects the greater donor ability of the sulfur atom. The MtN and M-S bond lengths for 1 and 2 are consistent with others reported in the literature.…”
The reactivity of the nitrido complexes (N(n)Bu(4))[Ru(N)(S(2)C(6)H(4))(2)] (1) and (N(n)Bu(4))[Os(N)(S(2)C(6)H(4))(2)] (2) (C(6)H(4)(SH)(2) = 1,2-benzenedithiol) toward electrophiles, R(+) (R = Me, Et, Ph(3)C), is described. While 1 yielded intractable mixtures of products, 2 could be cleanly alkylated. The synthesis of 1 has been reported previously (Z.Naturforsch. 1987, 42B, 341); complex 2 can be synthesized by treating (N(n)Bu(4))[Os(N)Cl(4)] with deprotonated 1,2-benzenedithiol in acetone/MeOH at 0 degrees C. Complexes 1 and 2 are isostructural and crystallize in the orthorhombic space group Pna2(1), Z = 8, with a = 36.881(6) Å, b = 9.402(2) Å, and c = 17.652(2) Å for 1 and a = 37.042(4) Å, b = 9.375(2) Å, and c = 17.671(2) Å for 2. The anions of both compounds consist of a five-coordinate mononuclear center with a distorted square-pyramidal geometry; a terminal nitrido ligand occupies the apical position and two chelating (S(2)C(6)H(4))(2)(-) ligands form the basal plane. Treatment of 2 with R(3)OBF(4) in CH(2)Cl(2) yields [Os(N)(S(2)C(6)H(4))(SC(6)H(4)SR)] (R = Me, 3; R = Et, 4) where one thiolate donor is alkylated. Alkylation of the sulfur of the 1,2-benzenedithiolate ligand was confirmed by NMR spectroscopy and X-ray crystallography (for 3). Complex 3.CH(2)Cl(2) crystallizes in the orthorhombic space group P2(1)2(1)2(1), Z = 4, with a = 8.551(1) Å, b = 10.772(2) Å, and c = 19.716(3) Å. In contrast, treatment of 2 with Ph(3)CPF(6) in CH(2)Cl(2) yields [Os(NCPh(3))(S(2)C(6)H(4))(2)] (5), whose (1)H and (13)C NMR spectra indicate that the terminal nitride is the site of electrophilic attack. X-ray crystallography further confirms the alkylation at the nitrogen atom; complex 5 crystallizes in the triclinic space group P&onemacr;, Z = 2, with a = 9.338(8) Å, b = 10.001(3) Å, c = 16.280(6) Å, alpha = 75.88(3) degrees, beta = 74.29(6) degrees, and gamma = 69.55(5) degrees.
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