176301-02-3Relevant articles and documents
Arene ruthenium(II) complexes coordinated by phosphino and two phenoxide groups in tris(2,6-dimethoxyphenyl)phosphine: crystal structure of (η6-1,2,3,4-Me4C6H2)Ru
Yamamoto, Yasuhiro,Sato, Ryoichi,Ohshima, Mayumi,Matsuo, Fumiko,Sudoh, Chihiro
, p. C68 - C70 (1995)
The title compound has been prepared from bis6-arene)ruthenium> (η6-arene = 1,2,3,4-C6Me4H2 (1a), p-cymene (1b) and tris(2,6-dimethoxyphenyl)phosphine (TDMPP).The crystal structure features a type of η3-phosphino-two phenoxides coordination.Reactions with its related phosphines, bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP) and (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) gave complexes with η2-phosphino-phenoxide and η1-phosphino coordinations, and trans-RuCl2(MDMPP)2, depending on phosphines and arene groups.Keywords: Ruthenium; Dealkylation; Tris(2,6-dimethoxyphenyl)phosphine
Reactions of [(η6-arene)RuCl2]2 with Aromatic Phosphines Containing Methoxy Groups in 2,6-Positions
Yamamoto, Yasuhiro,Sato, Ryoichi,Matsuo, Fumiko,Sudoh, Chihiro,Igoshi, Toshiaki
, p. 2329 - 2336 (2008/10/09)
Reactions of [(η6-arene)RuCl2]2 1 (arene = p-cymene (a), 1,2,3,4-Me4C6H2 (b), 1,2,3-Me3C6H2 (c)) with tris(2,6-dimethoxyphenyl)phosphine (TDMPP) led to loss of two molecules of CH3Cl to give (η6-arene)Ru[{2-O-C6H3-6-OMe} 2{C6H3(OMe)2-2,6}], 2a-c, which contains a trihapto ligand (η3-P,O,O) derived from TDMPP, whereas the 1,3,5-Me3C6H3 (1d), 1,2,3,5-Me4C6H2 (1e), and C6Me6 (1f) complexes did not react with TDMPP. The structures of 2a and 2b were confirmed by X-ray analyses: for 2a, a = 11.691(2) A, b = 15.228(2) A, c = 10.320(1) A, α = 95.93(1)°, β = 113.783(9)°, γ = 83.86(1)°, triclinic, P1, Z = 2, R = 0.051; for 2b, a = 17.79(2) A, b = 15.43(1) A, c = 20.93(1) A, β = 91.25(8)°, monoclinic, P21/n, Z = 8, R = 0.056. Bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP) reacted with 1a, 1b, and 1d at room temperature to give (η6arene)-RuCl[PPh(2-O-C6H3-6-OMe){C 6H3(OMe)2-2,6}], 3a,b,d, which contains a dihapto (η2-P,O) ligand derived from BDMPP by an X-ray analysis of 3a: a = 12.33(1) A, b = 14.246(8) A, c = 11.236(9) A, α = 91.47(8)°, β = 117.28(6)°, γ = 111.70(6)°, triclinic, P1, Z = 2, R = 0.040. A similar reaction with 1f recovered the starting materials, but that in refluxing MeCN produced [η6-C6Me6)Ru[PPh(2-O-C6H 3-6-OMe}2], 4f, containing a trihapto (η3-P,O,O) ligand derived from BDMPP. Complex 1d reacted with BDMPP at reflux in MeCN/CH2Cl2 and resulted in a loss of an arene ring to give a five-coordinate complex, Ru[η2-P,O-PPh(2-O-C6H3-6-OMe){C 6H3-(OMe)2-2,6}]2(MeCN), 5. Treatment of (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) with If gave (η6-C6Me6)RuCl[η 2-P,O-PPh2(2-O-C6H3-6-OMe)], 6f, and that with 1b gave (η6-1,2,3,4-Me4C6H 2)RuCl[η2-P.O-PPh2(2-O-C6H 3-6-OMe}], 6b, and (η6-1,2,3,4-Me4C6H2)RuCl 2[η1-P-PPh2{C6H 3(OMe)2-2,6}], 7b. The phosphine ligand of 6b acted as a bidentate ligand derived from MDMPP: a = 8.074(4) A, b = 16.816(3) A, c = 18.916(4) A, β = 94.05(3)°, monoclinic, P21/n, Z = 4, R = 0.051. Transformation of 7b to 6b readily occurred accompanying an elimination of MeCl. Reaction of la with MDMPP eliminated an arene ring to give the octahedral compound RuCl2[η2-P,OMe-PPh2{C6H 3(MeO)2-2,6}]2, 8. An X-ray analysis of 8 showed that two MDMPP ligands were in a cis-position: a = 10.596(14) A, b = 27.586(12) A, c = 13.036(8) A, β = 108.17(7)°, monoclinic, P21/n, Z = 4, R = 0.035.
