200880-91-7

Upstream product

• 14898-67-0 ruthenium(III) chloride trihydrate 
• 29679-67-2 N,N-dimethyl-2-diphenylphosphinoethylamine 
• 15529-49-4 tris(triphenylphosphine)ruthenium(II) chloride 

Relevant academic research and scientific papers

Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis, trans-bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)

The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh 2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 31.4866, c = 31.0540 ?; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24-2.26 ?), but the Ru-N bonds (2.37-2.42 ?) are 0.2 ? longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40±0.02 × 10-4 s-1 for the first step, and 3.29±0.03 × 10-5 s-1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.

Chelate ring-opening aminophosphine complexes of ruthenium(II)

The preparations and X-ray crystal structures of the Ru(II) aminophosphine complexes trans, cis-[RuCl2(H(Bz)NCH2CH2PPh2-N,P) 2] (1), trans, cis-[RuCl2(H2NCH2CH2PPh 2-N,P)2] (3) and [(η6-C6H6)Ru(PPh2CH 2CH2NMe2-N,P)Cl][PF6] (5) are described. Complexes 1 and 3 are octahedral and contain a marked distortion of the Cl-Ru-Cl axis from linearity. Complex 3 undergoes facile chelate ring-opening in DMSO and CH3CN solutions to give complexes containing one chelated aminophosphine ligand and one pendant ligand coordinated only through P. The X-ray structure of trans, cis-[RuCl2(DMSO-S)2(H2NCH2CH 2P(O)Ph2-N,O)] (4) containing an oxidised aminophosphine ligand is also reported.

Synthesis and reactivity of Ru(II) complexes containing the phosphino-amine Ph2PCH2CH2NMe2

RuCl3 · 3H2O reacts with 2 equiv. of Ph2PCH2CH2NMe2 in the presence of Zn to the neutral complex Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)2Cl2 (1). Alternatively, 1 is also obtained by the reaction of RuCl2(PPh3)3 with 2 equiv. of Ph2PCH2CH2NMe2. Compound 1 crystallizes in the space group P21 (No. 4) with a = 11.009(3), b = 11.007(4), c = 16.999(4) A, β = 106.22(2)° and Z = 2. The hemilabile nature of the Ph2PCH2CH2NMe2 ligand in 1 is revealed by the reaction with CO and HC ≡ CPh affording complexes Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)-(κ1(P)-Ph2PCH2CH 2NMe2)(Cl)2(CO) (2) and Ru(κ2(P,N)-Ph2PCH2CH2NMe 2) (κ1(P)-Ph2PCH2CH2NMe 2)(Cl)2(=C=CHPh) (3). Halide abstraction from 1 with NaBPh4 affords the five-coordinate cationic complex [Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)2Cl]+ [BPh4]- (4) which crystallizes in the space group Pbca (No. 61) with a = 21.806(4), b = 19.683(4), c = 26.405(5) A, and Z = 8. Compound 4 reacts readily with CH3CN, CO and HC ≡ CR (R = Ph, SiMe3, n-Bu) to give the cationic complexes [Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)2(Cl)-(CH3CN)]+ (5), [Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)2(Cl)(CO)]+ (6), and [Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)2(Cl)(=C=CHR)]+ (7-9). Compound [Ru(κ2(P,N)-Ph2PCH2CH2NMe 2)2(Cl)(CO)]+ [BPh4]- (6a) one of the two stereoisomers 6a and 6b crystallizes in the space group P1 (No. 2) with a = 11.637(3), b = 15.012(3), c = 15.306(3) A, α = 96.34(1), β = 98.32(1), γ = 98.73(1)° and Z = 2 and the isomeric compound 6b crystallizes in the space group P21/c (No. 14) with a = 20.445(2), b = 14.198(2), c = 19.717(2) A, β = 94.66(1)° and Z = 4. 1 catalyzes the dimerization of HC ≡ CPh to Z- and E-butenynes.