Organometallics p. 695 - 704 (1983)
Update date:2022-09-26
Topics:
Letts, John B.
Mazanec, Terry J.
Meek, Devon W.
Treatment of RuCl3·3H2O with the triphosphine ligands PhP(CH2CH2CH2PR2)2 (ttp, R = Ph; Cyttp, R = c-C6H11) produces the complexes [RuCl2(ttp)]x, 1, and RuCl2(Cyttp), 2, respectively. The ttp complex is polymeric whereas the Cyttp product is monomeric, presumably due to steric effects of the larger cyclohexyl (Cy) group. Treatment of 1 with carbon monoxide gives cis and trans carbonyl complexes, depending on the method of preparation; only a trans-dichloro carbonyl complex was obtained in the case of Cyttp. On the basis of infrared data (v(S-O) 1280, 1112 cm-1), the SO2 adduct of 2 has a planar geometry around the sulfur atom. Both chloride ligands of 1 can readily be substituted with CH3CN or CO by using Tl+ as a halogen scavenger; the acetate ion replaces only one chloride in the absence of Tl+. Treatment of 1 with NaBH4 produces RuH(η2-BH4)(ttp), which undergoes substitution reactions to yield the cationic hydrido ligand complexes [RuH(L)(L′)(ttp)]Y (L = P (OCH3)3, PF3, CO, NCCH3; L′ = P(OCH3)3, NCCH3, CO; Y = BF4) by treatment with HBF4 and the appropriate ligands. If the ligand substitution reactions are performed in basic solutions, the ligand dihydrido complexes RuH2(L)(ttp) result. The ruthenium(0) complexes Ru(CO)2(ttp), 10, and Ru(CO)2(Cyttp), 11, can be prepared by (i) Na/Hg reduction of 1 or 2, (ii) reduction of the dicarbonyl complexes [Ru(CO)2(ttp)][BF4]2 or [RuH(CO)2(ttp)]BF4, or (iii) triphosphine substitution of Ru3(CO)12. The complex Ru(CO)2(Cyttp), 11, undergoes oxidative addition reactions with halogens and acids to form the cationic, six-coordinate ruthenium(II) dicarbonyls [RuX(CO)2(ttp)]Y (XY = HCl, HBr, HBF4, Cl2, Br2) and with molecular oxygen to give Ru(CO3)(CO)(Cyttp). The preparation and characterization of these new ruthenium(II) and ruthenium(0) triphosphine complexes are reported, and structures are proposed on the basis of their conductivity, elemental compositions, and infrared, 1H, 31P, and 19F NMR spectroscopy.
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Doi:10.1246/bcsj.69.2281
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