Synthesis, Structure, and Reactivity of Ruthenium and Osmium Nitrido Complexes with 1,2-Benzenedithiolate Ligands:  N- versus S-Alkylation

Abstract

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.

Vicinal Dinitridoruthenium‐Substituted Polyoxometalates γ‐[XW10O38{RuN}2]6− (X=Si or Ge)

“…Previously,78 we arrived at the same conclusion for polyoxometalates γ‐[XW 10 O 36 ] ( n –4)− with X=P 5+ , Si 4+ , Al 3+ , and S 6+ , that is, X from the same‐row elements. The ruthenium–nitrido bond length is almost identical in both species (1.594(10) Å in 1 a , 1.612(11) Å in 1 b ), and falls well within the relatively narrow range of values reported for Ru VI N (from 1.57 Å79 to 1.62 Å,80 except for two complexes at 1.66 Å32, 39). The average rutheniumoxygen bond lengths are 1.944(8) Å (RuO Ru ), 2.002(8) Å (RuO W ), and 2.696(8) Å (RuO Si ) for 1 a , 1.963(8) Å (RuO Ru ), 2.013(8) Å (RuO W ), and 2.523(8) Å (RuO Ge ) for 1 b .…”

“…Previously, [78] we arrived at the same conclusion for polyoxometalates g-[XW 10 O 36 ] (n-4)À with X = P 5 + , Si 4 + , Al 3 + , and S 6 + , that is, X from the same-row elements. The ruthenium-nitrido bond length is almost identical in both species (1.594(10) in 1 a, 1.612(11) in 1 b), and falls well within the relatively narrow range of values reported for Ru VI ÀN (from 1.57 [79] to 1.62 , [80] except for two complexes at 1.66 [32,39] With structures so similar, it is more than likely that the reactivities of 1 a and 1 b are identical. Therefore, the study presented here concentrates mainly on the silicon derivative 1 a.…”

(Nitrido)ruthenium(VI) and ‐osmium(VI) Complexes with Catecholate Auxiliaries: Synthesis, Structure, and Conversion into a (Phosphoraniminato)osmium(V) Complex

“…In the IR spectra of 1a , 1b , 2a and 2b , sharp and intense bands, ascribable to ν Ru≡N /ν Os≡N appear at 1049 ( 1a ) and 1051 cm −1 ( 2a ) for the ruthenium species and at 1093 ( 1b ) and 1097 cm −1 ( 2b ) for the osmium species. The ν M≡N frequency of 1a / 1b is appreciably higher than the corresponding frequency of the sulfur analogues [N n Bu 4 ][M VI N(S 2 C 6 H 4 ) 2 ] (M = Ru, Os; S 2 C 6 H 4 = 1,2‐benzenedithiolate; ν Ru≡N = 1024 cm −1 , ν Os≡N = 1063 cm −1 ) reported by Sellmann and co‐workers 10. The study of the effect of catecholate auxiliaries on the M≡N bond by comparing the ν M≡N frequencies of 1a and 2a , or 1b and 2b , is complicated by the different counter‐cations in the nitrido complexes.…”

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…These complexes are most numerous for Ru and Os; to date no Fe analogs have been synthesized. For ruthenium and osmium, type II species are known with many different types of equatorial ligands: halogens, [105][106][107][108][109][110][111][112] alkyl, [113][114][115][116][117][118][119][120][121][122] Nor O-donors, [55,[123][124][125][126][127][128][129] and thiolates [130][131][132][133][134][135] are known. Reactivity of these species is similar to those of type I, though it should be mentioned that the [OsNCl 4 ] -anion has been recently used as a cocatalyst (along with FeCl 3 ) for the oxidation of alkanes.…”