98535-96-7Relevant academic research and scientific papers
Reactivity of Binuclear Pyrazolate-bridged Rhodium Complexes with Isocyanides. Molecular Structure of t)2-(μ-Ph2PCH2PPh2)2>BF4 (pz = pyrazolate)
Carmona, Daniel,Oro, Luis A.,Perez, Pedro L.,Tiripicchio, Antonio,Tiripicchio-Camellini, Marisa
, p. 1427 - 1434 (2007/10/02)
The CO groups of CIO4 (pz = pyrazolate, dppm = Ph2PCH2PPh2) have been gradually substituted by reaction with isocyanides CNR (R = But or C6H4Me-p) to give CIO4 t (3) or C6H4Me-p (4)> via CIO4 t (1) or C6H4Me-p (2)> and, finally, CIO4 t (7) or C6H4Me-p (8)> via CIO4 t (5) or C6H4Me-p (6)>.The CO bridging groups of (1), (2), (5), and (6) are ketonic carbonyls according to their spectroscopic properties.The reactivity of CIO4 (dpam = Ph2AsCH2AsPh2) with isocyanides was studied for comparison.The structure of the BF4- analogue of (7), t)2(μ-dppm)2>BF4 (7b), has been determined by X-ray diffraction methods.Crystals are monoclinic, space group P21/n with unit-cell parameters a = 20.347(8), b = 21.221(8), c = 14.514(6) Angstroem. β = 94.11(2) deg, and Z = 4.The structure has been solved from diffractometer data by Patterson and Fourier methods and refined by block-matrix least squares to R = 0.0630 for 4 969 observed reflections.In the cationic complex the two Rh atoms, at a distance of 2.829(3) Angstroem, are connected by a triple bridge, involving two dppm ligands and the pyrazolate anion.
Pyrazolate A-Frame Rhodium Complexes. Crystal Structures of and
Oro, Luis A.,Carmona, Daniel,Perez, Pedro L.,Esteban, Montserrat,Tiripicchio, Antonio,Tiripicchio-Camellini, Marisa
, p. 973 - 980 (2007/10/02)
New complexes of formula +, having the A-frame type structure with different pyrazolate-type groups L as bridgehead ligand, have been prepared from trans-(dppm = Ph2PCH2PPh2).Iodine undergoes transannular oxidative addition to to produce rhodium(II) complexes with direct rhodium-rhodium bonds.The crystal structures of the complexes and (dmpz = 3,5-dimethylpyrazolate) have been determined by X-ray methods.The former crystallises in the monoclinic space group P21/a with unit-cell dimensions a = 22.560(9), b = 26.649(9), c = 10.221(7) angstroem, β = 102.68(3) deg, and Z = 4.The structure has been refined to R = 0.072 on the basis of 4342 observed reflections.The latter crystallises in the monoclinic space group P2/n with a = 16.855(6), b = 14.713(3), c = 14.008(4) angstroem, β = 90.66(2) deg, and Z = 2.The structure has been refined to R = 0.078 (3048 observed reflections).In both complexes two rhodium atoms are triply bridged by two molecules of dppm and by a dmpz ligand through its nitrogen atoms.In the first complex each Rh atom has a square-planar co-ordination, in the second the oxidative addition of iodine results in a change in co-ordination to octahedral and formation of a metal-metal bond .
Oro, Luis A.,Carmona, Daniel,Perez, Pedro L.,Esteban, Montserrat,Tiripicchio, Antonio,Tiripicchio-Camellini, Marisa
, p. 973 - 980 (2007/10/02)
New complexes of formula +, having the A-frame type structure with different pyrazolate-type groups L as bridgehead ligand, have been prepared from trans-(dppm = Ph2PCH2PPh2).Iodine undergoes transannular oxidative addition to to produce rhodium(II) complexes with direct rhodium-rhodium bonds.The crystal structures of the complexes and (dmpz = 3,5-dimethylpyrazolate) have been determined by X-ray methods.The former crystallises in the monoclinic space group P21/a with unit-cell dimensions a = 22.560(9), b = 26.649(9), c = 10.221(7) angstroem, β = 102.68(3) deg, and Z = 4.The structure has been refined to R = 0.072 on the basis of 4342 observed reflections.The latter crystallises in the monoclinic space group P2/n with a = 16.855(6), b = 14.713(3), c = 14.008(4) angstroem, β = 90.66(2) deg, and Z = 2.The structure has been refined to R = 0.078 (3048 observed reflections).In both complexes two rhodium atoms are triply bridged by two molecules of dppm and by a dmpz ligand through its nitrogen atoms.In the first complex each Rh atom has a square-planar co-ordination, in the second the oxidative addition of iodine results in a change in co-ordination to octahedral and formation of a metal-metal bond .
