85848-64-2Relevant articles and documents
Synthesis and Structure of η4-Enone Complexes of Ruthenium(0)
Marcuzzi, Alessandro,Linden, Anthony,Philipsborn, Wolfgang von
, p. 976 - 987 (2007/10/02)
A variety of 4-enone)> complexes (L = phosphines, phosphites, and arsines, enone = (E)-4-phenylbut-3-en-2-one) have been synthesized. 1H, 13C-, and 31P-NMR spectra are reported and the X-ray structures of two Ru complexes with L = Ph3P (7), Et3P (10) and one Fe complex with L = Ph3P (14) are presented.All three compounds crystallize in the same monoclinic space group P21/n with a = 10.575(2) Angstroem, b = 9.213(2) Angstroem, and c = 27,608(5) Angstroem, β = 100,04(2) deg, Z = 4 for 7, a = 10,276(3) Angstroem, b = 12,935(3) Angstroem, and c = 14,854(2) Angstroem, β = 96,96(2) deg, Z = 4 for 10, and a = 10,492(2) Angstroem, b = 9,232(3) Angstroem, and c = 27,129(3) Angstroem, β = 98,67(2) deg, Z = 4 for 14.The structures of the Ru complexes are compared with the Fe analogues.In the case of M = Ru and L = (EtO)3P, (MeO)3P, and (i-PrO)3P (9, 11, and 13, respectively) stereoisomers could be detected by 31P-NMR at room temperature, which arise from rotation at the coordinated metal centre.
Axial-equatorial isomerism in the complexes M(CO)4(L) (M = Fe, Ru, Os; L = group 15 ligand). Crystal structures of ax-Ru(CO)4(AsPh3), ax-Ru(CO)4(SbMe3), and eq-Os(CO)4(SbPh3)
Martin, Lillian R.,Einstein, Frederick W. B.,Pomeroy, Roland K.
, p. 2777 - 2785 (2008/10/08)
The compounds M(CO)4(L) (M = Fe, Ru, Os; L = EPh3, E = P, As, Sb; L = PMe3, P(OCH2)3CMe. M = Ru, Os; L = SbMe3) have been synthesized from L and M(CO)5. The crystal structures of ax-Ru(CO)4(AsPh3), ax-Ru(CO)4(SbMe3), and eq-Os-(CO)4(SbPh3) have been determined by X-ray crystsllography. ax-Ru(CO)4(AsPh3): space group P1; a = 10.605 (3), b = 11.068 (4), c = 9.979 (3) ?; α = 113.57 (3), β = 93.14 (3), γ = 91.47 (3)°; Z = 2; R1 = 0.020, R2 = 0.021 (1650 observed reflections); AsPh3 in an axial position of the trigonal-bipyramidal coordination sphere, Ru-As = 2.461 (1) ?. ax-Ru(CO)4(SbMe3): space group R3, a = 10.378 (1), c = 9.632 (1) ?; Z =_3; R1 = 0.023, R2 = 0.030 (523 observed reflections); SbMe3 axial, Ru-Sb = 2.619 (1) ?. eq-Os(CO)4(SbPh3): space group P1; a = 11.123 (2), b = 11.284 (4), c = 12.714 (4) ?; α = 129.29 (2), β = 102.35 (2), γ = 102.45 (2)°; Z = 2; R1 = 0.019, R2 = 0.021 (3115 observed reflections); SbPh3 equatorial, Os-Sb = 2.612 (2) ?. Infrared spectroscopy revealed that in solution many of the complexes exhibited axial - equatorial isomerism. The tendency to give the less common equatorial isomer was Ru > Os > > Fe, Sb > As > P, Ph > Me, and P(OCH2)3CMe > PMe3, PPh3. The order for the group 15 element was rationalized in terms of the σ-donor ability of the element: in agreement with theoretical predictions, weaker donors prefer the equatorial site. The π-bonding ability of the ligands may also be important in determining the other trends. Carbon-13 NMR spectra, which revealed the isomers were in rapid equilibrium in solution, were also recorded.
