Ligand displacement reactions. Part V. The mechanisms of displacement of bidentate olefins from olefin(tetramethyl-1,4-benzoquinone)-nickel(0) complexes by trimethyl phosphite

Author(s):  
A. Pidcock ◽  
G. G. Roberts
1979 ◽  
Vol 89 (4) ◽  
pp. 1050-1057 ◽  
Author(s):  
Alosius F. Hepp ◽  
Richard S. Himmelwright ◽  
Nancy C. Eickman ◽  
Edward I. Solomon

1995 ◽  
Vol 73 (7) ◽  
pp. 1102-1110 ◽  
Author(s):  
Broer de Groot ◽  
Hilary A. Jenkins ◽  
Stephen J. Loeb ◽  
Shannon L. Murphy

Ruthenium(II) complexes of the thiacyclophane ligands 2,5,8-trithia[9]-o-cyclophane (TT[9]OC) and 5-oxa-2,8-dithia[9]-o-cyclophane (ODT[9]OC) were synthesized by ligand displacement reactions employing RuCl2(DMSO)4, RuCl2(PPh3)3, and RuHCl(PPh3)3 as starting materials. X-ray crystal structures of two of these complexes, RuCl2(DMSO)(TT[9]OC) and RuCl2(PPh3)(ODT[9]OC), demonstrate how TT[9]OC and ODT[9]OC bind to Ru(II). RuCl2(DMSO)(TT[9]OC) crystallized as the DMSO solvate in the orthorhombic space group Pbca with a = 19.590(5), b = 16.849(4), c = 13.149(4) Å, V = 4340(3) Å3, and Z = 8. The structure refined to R = 5.27% and Rw = 6.27% for 2472 reflections with Fo2 > 3σ(Fo2). RuCl2(PPh3)(ODT[9]OC) crystallized as a ClCH2CH2Cl solvate in the monoclinic space group P21/c with a = 7.912(1), b = 22.419(5), c = 18.794(3) Å, β = 101.12(1),° V = 3271.2(9) Å3, and Z = 4. The structure refined to R = 4.96% and Rw = 5.14% for 1800 reflections with Fo2 > 3σ(Fo2). Both compounds are octahedral with the thiacyclophane ligand bound through three donor atoms in a facial coordination mode, cis chlorine atoms, and the unique ancillary ligand, DMSO or PPh3, bound trans to the central S or O donor of the macrocycle. The X-ray structures support 1H NMR spectral evidence which shows that the ligands are bound in an "endo" mode for L = DMSO and in an "exo" mode when L = PPh3. The reaction of RuHCl(PPh3)3 with TT[9]OC yields the ruthenium hydride complex RuHCl(PPh3)2(TT[9]OC). 1H and 31P NMR spectroscopy are consistent with an octahedral species for which the macrocycle occupies only two coordination sites acting as a bidentate η2-chelating ligand. Keywords: thioether, macrocycle, hydride, crystal structure.


2010 ◽  
Vol 20 (3) ◽  
pp. 174-176 ◽  
Author(s):  
Dmitrii I. D’yachikhin ◽  
Fedor M. Dolgushin ◽  
Ivan A. Godovikov ◽  
Igor T. Chizhevsky

1973 ◽  
Vol 49 (1) ◽  
pp. C33-C34 ◽  
Author(s):  
A.J.P. Domingos ◽  
B.F.G. Johnson ◽  
J. Lewis

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