88867-61-2Relevant academic research and scientific papers
Metal-metal interactions in binuclear complexes. Structural characterization of isomers resulting from apparent internal oxidative addition of a platinum-chlorine bond to a rhodium(I) center
Balch, Alan L.,Guimerans, Rosalvina R.,Linehan, John,Olmstead, Marilyn M.,Oram, Douglas E.
, p. 1445 - 1451 (2008/10/08)
The face-to-face complex trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2, 1, isomerizes to trans-Rh-(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl upon heating in chloroform or upon treatment with a small amount of Ph2AsCH2PPh2. Metathesis of 1 with iodide produces trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI, and the bromo analogue has been prepared similarly. trans-Rh(CO)Cl2(μ-Ph2AsCH2PPh 2)2-trans-PtCl·2CH2Cl2, 2, crystallizes in the monoclinic space group P21/c with a = 17.563 (4) A?, b = 14.995 (4) A?, c = 21.338 (4) A?, β = 105.90 (2)°, V = 5404 (2) A?3, and Z = 4, at 140 K. The structure was refined to a conventional R value of 0.051 using 6017 unique reflections and 334 parameters. trans-Rh(CO)I2(μ-Ph2AsCH2PPh 2)2-trans-PtI-CH2Cl 2·2CHCl3, 4, crystallizes in the orthorhombic space group Pbca with a = 17.808 (8) A?, b = 19.488 (8) A?, c = 35.228 (15) A?, V = 12225.6 (9) A?3, and Z = 8 at 140 K. The structure was refined to a conventional R value of 0.092 using 5001 unique data and 344 parameters. Both structures are similar with a six-coordinate rhodium atom (ligands: two As, CO, two Cl or two I, Pt) and a four-coordinate platinum (ligands two P, Rh, Cl or I) joined by a Pt-Rh bond (2.692 (1) A? in 2 and 2.737 (3) A? in 4). The carbonyl group in both complexes displays a subtle tilting toward the platinum atom. This results in a significant lowering (20-40 cm-1) of the carbonyl stretching frequency.
Preparation and structure of mono- and binuclear complexes of (diphenylarsino)(diphenylphosphino)methane including the x-ray crystal structure of trans-Rh(CO)Cl(μ-Ph2AsCH2PPh2) 2-cis-PtCl2
Balch, Alan L.,Guimerans, Rosalvina R.,Linehan, John,Wood, Fred E.
, p. 2021 - 2026 (2008/10/08)
The reactions of (diphenylarsino)(diphenylphosphino)methane with (1,5-COD)PtX2 (1,5-COD = 1,5-cyclooctadiene; X = Cl, Br, I) or with Rh2(CO)4(μ-Cl)2 to yield Pt(dapm)X2 (chelating dapm), Pt(dapm)2X2, or trans-Rh(dapm)2(CO)Cl (monodentate dapm) are reported. In solution Pt(dapm)2X2 can ionize to form [Pt(damp)2X]X or [Pt(dapm)2]X2. The degree of ionization depends on X and on the solvent. trans-Rh(dapm)2(CO)Cl reacts with Rh2(CO)4(μ-Cl)2 to yield the face-to-face dimer Rh2(μ-dapm)2(CO)2Cl2 as a mixture of head-to-head (P trans to P) and head-to-tail (P trans to As) isomers. Pt(dapm)2Cl2 reacts with Pt(dibenzylideneacetone)2 to form head-to-head and head-to-tail isomers of Pt2(μ-dapm)2Cl2. These react with carbon monoxide to form Pt2(μ-dapm)2(μ-CO)Cl2. Rh2(CO)4(μ-Cl)2 reacts with Pt(dapm)2Cl2 to form trans-Rh(CO)Cl(μ-dapm)2-cis-PtCl2. This orange complex crystallizes in the space group P21/c (No. 14) with a = 18.760 (3) A?, b = 11.610 (3) A?, c = 22.954 (6) A?, β = 92.81 (2)°, and Z = 4 at 140 K. The structure was refined to a conventional R value of 0.038 by using 6415 significant reflections and 572 parameters. The structure consists of face-to-face planar Rh(CO)ClAs2 and PtP2Cl2 units. The nonbonded Pt?Rh distance is 3.043 (1) A?.
