Triply-bridged diruthenium(II) 1,4-bis(diphenylphosphino)butane (dppb) and (R)-2,2 '-bis(diphenylphosphino)-1,1 '-binaphthyl (binap) complexes, including structural characterisation of [(dppb)ClRu(mu-D2O)-(mu-Cl)(2)RuCl(dppb)], [(eta(2)-H-2)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] and the [(dppb)ClRu(mu-Cl)(3)RuCl(dppb)](-) anion
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| Authors: | MacFarlane, KS; Thorburn, IS; Cyr, PW; Chau, DEKY; Rettig, SJ; James, BR |
| Year: | 1998 |
| Journal: | Inorganica Chimica Acta 270: 130-144 Article Link (DOI) |
| Title: | Triply-bridged diruthenium(II) 1,4-bis(diphenylphosphino)butane (dppb) and (R)-2,2 '-bis(diphenylphosphino)-1,1 '-binaphthyl (binap) complexes, including structural characterisation of [(dppb)ClRu(mu-D2O)-(mu-Cl)(2)RuCl(dppb)], [(eta(2)-H-2)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] and the [(dppb)ClRu(mu-Cl)(3)RuCl(dppb)](-) anion |
| Abstract: | Several triply-bridged diruthenium(II)(1,4-bis(diphenylphosphino)butane) complexes were synthesised and characterised by elemental analysis, UV-Vis, NMR and IR spectroscopies, The solid-state structures of [(dppb)ClRu(mu-D2O)(mu-Cl)(2)RuCl(dppb)] (1), [(eta(2)-H-2) (dppb)Ru(mu-Cl)(3)RuCl(dppb)] (2) and [TMP][(dppb)ClRu(mu-Cl)(3)RuCl(dppb)] (3) were established by X-ray crystallographic analyses (TMP=1,1,3-trimethyl-2,3-dihydroperimidinium; dppb = Ph2P(CH2)(4)PPh2). Crystals of 1.1.5C(6)D(6), 2.1.5C(7)D(8) and 3.2Me(2)CO.2H(2)O are all monoclinic, space groups P2(1)/c, P2(1)/n and C2/c, respectively, with Z=4: a=16.8681(6), b=13.3542(4), c=26.4966(7) Angstrom, beta=91.877(1)degrees for 1.1.5C(6)D(6); a = 19.8123(1), b=14.5246(2), c = 22.1803(1) Angstrom, beta=106.58(1)degrees for 2.1.5C(7)D(8); a=21.596(2), b=16.019(2), c=22.317(2) Angstrom, beta=106.15(1)degrees for 3.2Me(2)CO . 2H(2)O. The structures of 1 and 2 were salved by direct methods while 3 was solved by heavy atom methods and all were refined by full-matrix least-squares procedures to R-1 = 0.0433, 0.0612 and R = 0.039 (wR(2) = 0.0709 (1), 0.1178 (2)) for 7751, 6757 and 5237 reflections with I greater than or equal to 2 sigma(I) for 1 and 2 and I greater than or equal to 3 sigma(I) for 3, respectively, Complex I was also studied in the solid-state by P-31 CP/MAS NMR spectroscopy. The bromo- and iodo-analogues of 1 were prepared, and these three species were screened as catalysts for hydrogenation of aldimines. The complexes [H2NR2][{RuCl(P-P)}(2)(mu-Cl)(3)] were synthesised by the addition of NR3 or [H2NR2]Cl to RuCl2(P-P)(PPh3), where P-P = dppb or (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) and R =Et, n-Bu or n-Oct. The syntheses of [(DMA)(2)H][(PPh3)(2)ClRu(mu-Cl)(3)RuCl(PPh3)(2)], [(py)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] and [(C2H4)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] were also accomplished (DMA = N,N-dimethylacetamide; py = pyridine). (C) 1998 Elsevier Science S.A. |
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