472958-27-3Relevant academic research and scientific papers
Synthesis and structural characterization of sulfur rich iron (II) carbonyl dimers: Facile reversible reaction with carbon monoxide
Carcer, Inigo Aguirre de,Heinekey, D. Michael
experimental part, p. 840 - 844 (2009/05/27)
The sulfur-rich iron carbonyl dimer complexes [Fe(CO)2(S′SiS2)]2 (2), and [Fe(CO)(S′SiS2)]2 (3) have been prepared. The [2Fe-2S] cores of the new complexes are planar. The binding mode of the tridentate sulfur ligand in complex 2 is facial with a S(thiolate)-Fe-S(thiolate) angle of 92°, while in complex 3, the S′SiS2 ligand binds the metal with a S(thiolate)-M-S(thiolate) angle of 120°. The Fe-Fe distance is reduced from 3.45 A? in complex 2 to 2.78 A? in the 32 electron dimer complex 3. Complexes 2 and 3 are at equilibrium in solution and can be readily interconverted by addition or removal of CO.
Highly soluble sulfur-rich [Ni(L)(siS3)] complexes containing the new ligand Bis(2-mercapto-3-trimethylsilylphenyl) sulfide(2-) (siS32-)
Sellmann, Dieter,Prakash, Raju,Geipel, Franz,Heinemann, Frank W.
, p. 2138 - 2146 (2007/10/03)
The new organosulfur ligands siS3-H2 [siS32- = bis(2-mercapto-3-trimethylsilylphenyl) sulfide(2-)] and caS3-H2 [caS32- = bis(2-mercapto-3-carboxyphenyl) sulfide(2-)] were synthesized from HS3-H2 [HS32- = bis(2-mercaptophenyl) sulfide(2-)], n-butyllithium, and Me3SiCl or CO2/H+. Reaction of siS3-H2 with Ni(ac)2·4H2O gave the air-stable and well-soluble trinuclear complex [Ni(siS3)]3 (1) whose structure was determined by X-ray crystallography. Reactions of complex 1 with nucleophiles L [L = PR3 (R = nPr, Ph, Cy), N2H4, StBu-, and Cl-] yielded the corresponding neutral or anionic complexes, which were isolated as [Ni(PR3)(siS3)] [R = nPr (2), Ph (3), Cy (4)], Bu4N[Ni(Cl)(siS3)] (5), Bu4N-[Ni(StBu)(siS3)] (6), and [Ni(N2H4)(siS3)] (8). The azido complex Et4N[Ni(N3)(siS3)] (7) was prepared from Me3SiN3 and the precursor chloro complex Et4N[Ni(Cl)(siS3)]. Reaction of 1 with NH3 yielded labile [Ni(NH3)(siS3)] (9), which was characterized in solution by 1H and 13C NMR spectroscopy. Analogously, 1 reacts with nicotinamide (NA) or diethylnicotinamide (NAEt2) to give, from equilibrium reactions, the corresponding mononuclear [Ni(L)(siS3)] complexes with L = NA, NAEt2. X-ray structure determinations showed that 1, 3, 4, 5, and 7 all exhibit tetrahedrally distorted planar [Ni(L)(siS3)] fragments. Complex 7 is the first structurally characterized azidonickel complex with a coligand having exclusively sulfur donors. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
