Structural Investigations of Sulfite-Bridged Binuclear Complexes of Platinum(II) and Palladium(II)

Abstract

Although analogous platinum(II) and palladium(II) compounds usually show similar chemical behaviour, different reaction products have been obtained on reaction of ethane-1,2-diamine bissulfitometallates(II) with the diaqua ethane-1,2-diamine metal(II) complexes of Pt and Pd. − The crystal structures of bis(µ-sulfito-1κS:2κO)bis[(ethane-1,2-diamine)-platinum(II)] trihydrate [(en)Pt(SO 2 O) 2 Pt(en)]·3 H 2 O (1) with parallel µ-(S:O) sulfite bridges, and of bis[(ethane-1,2-diamine)-µ-(S:O)-sulfitopalladium(II)] trihydrate [(en)Pd(SO 2 O)-(OO 2 S)Pd(en)]·3 H 2 O (2) with antiparallel bridges, have been determined by single-crystal X-ray structure analyses. In both compounds the complex units are held together mainly by a complicated network of hydrogen bonds including the hydrate water molecules. − In contrast to the complex molecules in 1 with parallel bridges, the complex units of 2 possess

Heterobimetallic Lantern Complexes That Couple Antiferromagnetically through Noncovalent Pt···Pt Interactions

“…The conformation of 5 is staggered, much like what is observed for 1 – 3 . The Pt···Pt distance of 3.0583(4) Å is exceptionally short, with only three examples reported that exhibit shorter − contacts between strictly Pt(II) centers as shown in Table . Despite having an exceptionally short Pt···Pt distance, 5 exhibits the longest S···S contacts between lanterns, with an average separation of 3.59(7) Å.…”

“…Found: C, 22.98; H, 2.47; N, 4.03%. UV−vis−NIR(CH 2 Cl 2 ) (λ max , nm (ε M , cm −1 M −1 )): 266(37,300), 395(405)(sh), 487(128), 520 (39), 573 (19), 1233 (5). Evans method (CDCl 3 ): 5.06 μ B .…”

Selective Two-Step Oxidation of μ2-S Ligands in Trigonal Prismatic Unit {Re3(μ6-C)(μ2-S)3Re3} of the Bioctahedral Cluster Anion [Re12CS17(CN)6]6–

“…The only method of their synthesis is the association of mononuclear fragments with sulfite anion in solution. For example, the following compounds were obtained this way: Ni[Co(en) 2 (SO 3 ) 2 ] 2 (H 2 O) 2 ·4H 2 O, [(en)Pt(SO 3 ) 2 Pt(en)]·3H 2 O, and [(en)Pd(SO 3 ) 2 Pd(en)]·3H 2 O . As one can see, there is a fundamental difference between this method and synthesis of the compound 3 .…”

“…On the basis of the literature data, we can assume that bridging SO 3 ligand appears in bands at 1070 and 864 cm –1 , and one more band at 1143–1157 cm –1 is overlapped with band from μ-SO 2 ligands. The band at about 1000 cm –1 corresponds to the vibrations of SO 2 groups. − …”

Stepwise Sulfite Reduction on a Dinuclear Ruthenium Complex Leading to Hydrogen Sulfide

“…Treatment of 1 with Oxone afforded the sulfite-bridged paramagnetic complex [(TpRu) 2 (μ-Cl)­(μ-pz)­(μ-SO 3 -κ 2 )] ( 5 ) in 86% yield (Scheme ) that was structurally characterized by X-ray crystallography (Figure ). Oxygenation of the sulfur atom resulted in elongation of the bridging S–O bond (1.830(6) Å), which is longer than that in [Pd­(NH 2 CH 2 CH 2 NH 2 )]­(μ-SO 3 -κ 2 ) (1.501(8) Å) . DFT calculations indicated that the electronic ground states of 1 and 5 are singlet and triplet, respectively (Figure S10).…”