36581-28-9Relevant academic research and scientific papers
Aryldiazenide complexes. Synthesis and X-ray structure of trans-chlorobis(triphenylphosphine)((p -methoxyphenyl)diazenido) rhodium tetrafluoroborate-bis(dichloromethane), [RhCl(PPh3)2(p-N2C6H 4OMe)][BF4]·2CH2Cl2
Einstein, Frederick W. B.,Jones, Richard H.,Zhang, Ya-Mei,Sutton, Derek
, p. 1004 - 1010 (2008/10/08)
The complex [RhCl(PPh3)2(p-N2C6H 4OMe)][BF4] (1) and its bis(acetone) and bis(dichloromethane) solvates (1·2Me2CO and 1·CH2Cl2) have been synthesized from the reaction of [RhCl(PPh3)2]2 with [p-N2C6H4OMe] [BF4] in acetone. The X-ray crystal structure of 1·2CH2Cl2 has been determined. 1·2CH2Cl2 crystallizes in the orthorhombic space group Pnma with a = 22.573 (3) A?, b = 21.961 (3) A?, c = 9.522 (2) A?, V = 4720 A?3, Z = 4, and Dcalcd = 1.16 g cm-3. The structure was solved by using 2181 observed reflections in the range 4° F = 0.044 (RwF = 0.052). The cation [RhCl(PPh3)2(p-N2C6H 4OMe)]+ is square-planar with a singly bent Rh-N2Ar moiety (Ar = p-C6H4OMe), consistent with the formal view that it is a complex of Rh(I) and N2Ar+. Important dimensions are Rh-N(1) = 1.793 (8) A?, N(1)-N(2) = 1.157 (11) A?, Rh-N(1)-N(2) = 179.4 (7)°, and N(1)-N(2)-C(aryl) = 141.3 (9)°. Complex 1 reacts with hydrogen chloride to form first the new cationic aryldiazene complex (4) with δ(NH) at 10.64, formulated as [RhCl2(PPh3)2(p-NHNC6H 4OMe)][BF4], and subsequently the known neutral aryldiazene complex RhCl3(PPh3)2(p-NHNC6H 4OMe) (3) with δ(NH) at 11.54. Complex 1 is transformed into the known neutral aryldiazenide complex RhCl2(PPh3)2(p-N2C6H 4OMe) (2) by LiCl, and the reaction is reversed with AgBF4. Reaction of 1 with PPh3 at low temperature forms an unstable green complex having v(NN) at 1659 cm-1 that is also formed in the reaction of RhCl(PPh3)3 with [p-N2C6H4OMe][BF4] and is tentatively identified as [RhCl(PPh3)3(p-N2C6H 4OMe)][BF4] as originally suggested by Baird and Wilkinson.
