“…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 M⋮N and M−S bond lengths for 1 and 2 are consistent with others reported in the literature. ,, 1 ORTEP diagrams of the anions of (N n Bu 4 )[Ru(N)(S 2 C 6 H 4 ) 2 ] ( 1 ) (left) and (N n Bu 4 )[Os(N)(S 2 C 6 H 4 ) 2 ] ( 2 ) (right) at the 50% probability level. Hydrogen atoms have been omitted for clarity.…”
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.
“…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 M⋮N and M−S bond lengths for 1 and 2 are consistent with others reported in the literature. ,, 1 ORTEP diagrams of the anions of (N n Bu 4 )[Ru(N)(S 2 C 6 H 4 ) 2 ] ( 1 ) (left) and (N n Bu 4 )[Os(N)(S 2 C 6 H 4 ) 2 ] ( 2 ) (right) at the 50% probability level. Hydrogen atoms have been omitted for clarity.…”
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.
“…The minor cis isomer has nitrido ligands on the same side of the molecule, while the major trans isomer has the nitrido ligands on opposite sides of the molecule. The ability of sulfur ligands to bridge osmium(VI) centers has been well established. ,, The interaction between the osmium atoms and the bridging sulfur is strong. This is demonstrated by our failure to prepare neutral, monomeric organoosmium(VI) thiolate complexes by the reaction of Os(N)(CH 2 SiMe 3 ) 2 (py)Cl with 1 equiv of NaSCH 2 Ph or by treatment of 5 with excess pyridine.…”
Primary, secondary, and tertiary alkanethiolate complexes of osmium(VI) possessing bridging thiolate ligands have been prepared and characterized. The complexes [Os(N)-(CH 2 SiMe 3 ) 2 (µ-SR)] 2 (R ) CH 2 CH 3 , CMe 3 , CHMe 2 , CH 2 CHMe 2 , CH 2 Ph) are synthesized by the reaction of [Os(N)(CH 2 SiMe 3 ) 2 Cl] 2 with alkali metal thiolates. They are air-and waterstable and unreactive toward nucleophiles and electrophiles. Anionic tetrathiolate and tetraalkoxide complexes of osmium(VI) have also been prepared and characterized. Reaction of [PPh 4 ][Os(N)Cl 4 ] with NaSCH 2 Ph or LiOCH 2 Ph in refluxing THF produces [PPh 4 ]-[Os(N)(SCH 2 Ph) 4 ] or [PPh 4 ][Os(N)(OCH 2 Ph) 4 ]. Thermolysis of [PPh 4 ][Os(N)(SCH 2 Ph) 4 ] gives benzyl disulfide, probably via reductive elimination, while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol upon heating in a β-hydrogen elimination reaction.
“…We have previously prepared heterobimetallic and heterotrimetallic with bridging oxo or sulfido groups through specific bridge-building reactions such as the reaction of organoosmium(VI) and organoruthenium(VI) chloro compounds [N(n-Bu) 4 ][M(N)R 2 Cl 2 ] with Ag 2 CrO 4 [4], AgReO 4 [5], or K 2 WS 4 [6]. The ruthenium compounds [N(n-Bu) 4 ][Ru(N)Me 2 Cl 2 ] also react with (trimethylsilyl)sulfido compounds M 0 (SSiMe 3 ) 2 L 2 (M 0 = Ni, Pd, Pt; L 2 = dppe, COD) to form the trimetallic species {Ru(N)Me 2 }(l 3 -S) 3 {M 0 L 2 } [7,8].…”
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