Highly Soluble Sulfur-Rich [Ni(L)(siS3)] Complexes Containing the New Ligand Bis(2-mercapto-3-trimethylsilylphenyl) Sulfide(2−) (siS32−)

Abstract

Keywords: Nickel / S ligands / Silicon / Hydrazine / NicotinamideThe new organosulfur ligands si S 3 -H 2 [ si S 3 2− = bis(2-mercapto-3-trimethylsilylphenyl) sulfide(2−)] and ca S 3 -H 2 [ ca S 3 2− = bis(2-mercapto-3-carboxyphenyl) sulfide(2−)] were synthesized from H S 3 -H 2 [ H S 3 2− = bis(2-mercaptophenyl) sulfide(2−)], n-butyllithium, and Me 3 SiCl or CO 2 /H + . Reaction of si S 3 -H 2 with Ni(ac) 2 ·4H 2 O gave the air-stable and well-soluble trinuclear complex [Ni( si S 3 )] 3 (1) whose structure was determined by X-ray crystallography. Reactions of complex 1 with nucleophiles L [L = PR 3 (R = nPr, Ph, Cy), N 2 H 4 , StBu − , and Cl − ] yielded the corresponding neutral or anionic complexes, which were isolated as [Ni(PR 3 )( si S 3 )] [R = nPr (2), Ph (3), Cy (4)], Bu 4 N[Ni(Cl)( si S 3 )] (5), Bu 4 N-[Ni(StBu)( si S 3 )] (6), and [Ni(N 2 H 4 )( si S 3 )] (8). The azido complex Et 4 N[Ni(N 3 )( si S 3 )] (7) was prepared from Me 3 SiN 3 and

Metallohosts with a Heart of Carbon

“…The latter contains one-sixth of a molecule of CH 2 Cl 2 , which is disordered about the 3̅ position (0,0,0), Wyckoff position a . The assembly of 1 and the chair conformation of the central Ni 3 S 3 core mimic observations on related systems. − Each O,N,S-donor set of the ligand binds in a tridentate mode to a square-planar Ni 2+ ion, and the S atom bridges two Ni centers. The bond lengths in the nickel coordination sphere are Ni1–O1 = 1.851(2) Å, Ni1–N1 = 1.887(3) Å, Ni1–S1 = 2.1870(10) Å, and Ni1–S1 ii = 2.2141(10) Å.…”

Cleavage of Ni-(μ2-S)-Ni Bridges in Dinuclear Nickel(II) Dithiolate Pincer Complexes and Related Reactions

“…In reaction 1, dinuclear species are converted to mononuclear products which retain attacking ligand L″, often a tertiary phosphine or cyanide 5–10. Reaction 2 with cyclic trinuclear reactants proceeds similarly to yield mononuclear complexes 11–14. Linear trinuclear reactants are cleaved to mononuclear or dinuclear products in reaction 3 15,16.…”

Synthesis and structural characterization of sulfur rich iron (II) carbonyl dimers: Facile reversible reaction with carbon monoxide

“…Fe 2 (CO) 9 (Strem), isopentyl nitrite (Aldrich), anthranilic acid (Aldrich), ethylene trithiocarbonate (Aldrich) and propylene oxide (Aldrich), were used as received. S 0 (SH) 2 and S 0 ( Si SH) 2 were prepared using slight modification of the literature procedures, as detailed below [11,[16][17][18]. [Fe(CO) 2 (S 0 S 2 )] 2 was prepared by reaction of [Fe(CO) 3 (PhCH@CHCOMe)] [22] with S 0 SH 2 .…”

“…1) were initially developed by Sellmann and coworkers, who prepared a series of MS 0 S 2 L complexes (M = Ni, Pt, Fe) [10][11][12]. The tridentate ligands S 0 S 2 and S 0 Si S 2 are structurally flexible.…”