Selective Azide Oxidation of 1,2-Bis(diphenylphosphino)benzene and Related Ethylenebis(phosphines) to Asymmetric Multifunctional Phosphorus Ligands and Formation of Rhodium(I) Complexes of These Ligands. Structural Characterization of the Prototypical Ligand 1-(((Trimethylsilyl)imino)diphenylphosphorano)-2-(diphenylphosphino)benzene and Its Rhodium(I) Complex: 1-Ph2PN(SiMe3)C6H4-2-(Ph2P)Rh(CO)Cl
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (15) , 4292-4300
- https://doi.org/10.1021/ic9514713
Abstract
Selective azide mono-oxidation of o-bis(phosphines) such as o-bis(diphenylphosphino)benzene and other bis(phosphines) with cis-substituents on a rigid backbone such as an ethylene structure occurs as the result of the steric control exerted during the azide oxidation (Staudinger) reaction process. The azides used were the trimethylsilyl, 4-cyanotetrafluorophenyl, benzyl, and diphenoxyphosphonyl azides. The prototypical ligand 1-Ph2PN(SiMe3)-2-(Ph2P)C6H4, 2, has been structurally characterized. Crystal data for 2: crystal dimensions, 0.38 × 0.38 × 0.57 mm; space group, monoclinic, P21/c, (No. 14); a = 11.093(5) Å, b = 14.898(5) Å, c = 18.811(2) Å, β = 102.76(2)°, V = 3031 Å3, Z = 4. Final R, Rw and GOF values were 0.068, 0.074, and 1.92 respectively. The PNSiMe3 angle was wide, 152.7(3)°, and the PN bond length short (1.529(5) Å) relative to arylated iminophosphoranes but in keeping with the trends for silylated analogs. The iminophosphorane center can be selectively transformed with other agents in a Wittig type reaction converting the azides to the monooxide, monosulfide, etc. The iminophosphoranophosphines are also good complexing agents and the Rh(I) complex derived from 2, 1-Ph2PN(SiMe3)-C6H4-2-(Ph2P)Rh(CO)Cl, 15 was structurally characterized. Crystal data for 15: crystal dimensions, 0.32 × 0.44 × 0.66 mm; space group, monoclinic, P21/c (No. 14); a = 13.793(3) Å, b = 12.622(11) Å, c = 20.436(6) Å, β = 105.93(2)°, V = 3421.2 Å3, Z = 4. Final R, Rw, and GOF values were 0.064, 0.061, and 1.45 respectively. The complex shows typical square planar geometry about Rh, a cis phosphine−CO relationship, and no exceptional steric crowding of the coordination site.Keywords
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