Structure of [1,2-bis(diphenylphosphino)ethane]chloro(η5-cyclopentadienyl)ruthenium(II)

Abstract

The asymmetric unit is comprised of a molecule of (r/5-Cp)RuCl(dppe), where dppe is 1,2-bis(diphenylphosphino)ethane, and a co-crystallized molecule of dppe group, a chloride ligand and the cyclopentadienyl ligand. The bond to Cl(1) measures 2.452 (2)/~ and bonds to the P atoms measure 2.275 (2) and 2.282 (2) A for Ru(1)--P(1) and Ru(1)--P(2), respectively.Within the cyclopentadienyl ligand we find the five C atoms to be essentially coplanar with a maximum out-of-plane displacement of 0.0123 A (mean deviation of 0.0079 A) and C---C bonds in the range 1.372 (8) to 1.421 (9)•. The Ru atom is 1.851/~ Acta Crystallographica Section C ISSN 0108-2701 ©1993REGULAR STRUCTURAL PAPERS 1457 from the centroid defined by the five C atoms of the Cp ring and is displaced slightly (approximately 0.08 A) towards the C(54) and C(55) atoms which are trans to Cl(1). Structural features of this complex resemble the chiral complex (r/5-Cp)RuCl(prophos), where prophos is a chiral derivative of dppe containing a methyl group on the ethylene bridge (Morandini, Consiglio, Straub, Ciani & Sironi, 1983). Bond lengths and angles within the coordination sphere of the Ru atom are also in good agreement with those reported for another (r/5-Cp)Ru n chloride complex containing dcpm. A principal difference between the two lies in the bite angle of the latter which, owing to the fact that it contains one atom less in the carbon bridge linking the two phosphine moieties, is remarkably acute [P--Ru--P= 69.57 (8) ° (Joslin, Mague & Roundhill, 1991)].Significantly, the nature of the ancillary R group bonded to P of the phosphine ligand appears to have only a minor influence on the coordination geometry about the transition-metal center. A comparison of the structures of complexes containing chelating phosphines with those containing monodentate phosphines such as ('r/5-Cp)RuCI(PR3)2 (R = Ph, Me) indicates that the P--Ru--P angle in those complexes containing chelating phosphines is acute, whereas in complexes containing either PMe3 or PPh3 the P--Ru--P angles are obtuse (Bruce, Wong, Skelton & White, 1981). C (2) C (3) .... C(15) CI(ll C1321 REGULAR STRUCTURAL PAPERSC(42) 0.4199 0.6288 0.9674 0.061 (2) C(43) 0.4296 0.7406 0.9353 0.061 (2Phenyl rings were refined as rigid groups using H atoms placed in idealized postious with fixed isotropic U = 0.08 .~2. The Tll reflection suffered from extinction and was therefore omitted during the refinement process. All structure calculations were performed with the SHELXTL-Plus system (Sheldrick, 1990).Acknowledgement is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research, and also to the Welch Foundation. We wish to thank especiaUy the Engelhard Corporation for their gift of ruthenium trichloride, and F. Cervantes-Lee for collecting the intensity data. AbstractThe tetranuclear ruthenium carbonyl hydride cluster, di-/z-carbonyl-undecacarbonyl-di#z-hydrido-tetrahedro-tetraruthenium(6Ru--Ru), crystallizes in a monoclini...

Heterobimetallic compounds [Ru(η5-Cp)(dppf)X] (X = Cl, Br, I and N3): synthesis, electrochemical analysis, and the crystal structure of [Ru(η5-Cp)(dppf)I] [dppf = 1,1′-bis(diphenylphosphino)ferrocene]

“…Table 2, and the average of the Ru-I bond lengths, 2.7228(5) Å is within the normal range 2.72-2.78 Å found for other related Ru(II) complexes [11]. Also, the average Ru-P bond length, 2.288 Å , is essentially the same as those reported for the chiral complexes, [Ru(g 5 The larger bite size of dppf forces a wider P(1)-Ru(1)-P(2) chelate angle as much as 97.08(4)°, close to that found for the [Ru(g 5 -Cp)(dppf)Cl] [95.01(4)°] [12], but much higher than that one for the [Ru(g 5 -Cp)(dppe)Cl] [83.48(2)°] [13][14][15]. The distances Ru(1)-I(1) and Ru (2) The cyclic voltammograms of the complexes (1), (2) and (3) [as shown in Fig.…”

Comparative reactivity studies of dppf-containing CpRuII and (C6Me6)RuII complexes towards different donor ligands (dppf=1,1′-bis(diphenylphosphino)ferrocene)

“…It shows a mononuclear Ru(II) capped by an g 5 -Cp ring, a chelating g 2 -dppf and a terminal chloride, thus completing a three-legged piano-stool configuration. The Ru-Cl bond distance of 2.4446 (12) A and Ru-P distances of 2.2871(12) and 2.2852 (12) A in 1 are virtually indistinguishable from those found in the dppe analogue, [CpRu(dppe)Cl] [29,30] (2.4466(7), 2.2688(7) and 2.2863 (7) A, respectively) [30]. The larger bite size of dppf forces a wider PRu-P chelate angle (95.01 (4) P-ring centroids-P of 4.81(7)° [7].…”

Ruthenium piano-stool complexes containing mono- or bidentate pyrrolidinylalkylphosphines and their reactions with small molecules

“…The PeN distances within the phosphine ligand (1.669(2)e1.715(2) Å) again follow a pattern where an increase in planarity about the nitrogen atoms leads to a shortening of the PeN bond. The complex [CpRuCl(dppe-k 2 P)], a structural analogue of 3, has RueP distances (2.275(2) Å and 2.282(2) Å) and a PeRueP bond angle (83.49 (4) ) [14] that are only slightly larger than those observed for 3 (2.2654(6) Å and 2.2626(6) Å, 81.45(2) ), suggesting the dipyrrolidinylphosphino group in I is perhaps close in size to the corresponding diphenylphosphino group in dppe. The cone angle for dppe has been estimated to be 125 [13], and so we might then expect the cone angle for ligand I to be about the same.…”