Dataset Information

Crystal structure of (OC)₅W(?-dppe)W(CO)₅.

ABSTRACT: The centrosymmetric title complex, [?-ethane-1,2-diylbis(di-phenyl-phosphane)-?²P:P']bis-[penta-carbonyl-tungsten(0)], [W₂(C₂₆H₂₄P₂)(CO)₁₀], consists of two W(CO)₅ moieties bridged by a bis-(di-phenyl-phosphan-yl)ethane (dppe) ligand. The W⁰ atom has a slightly distorted octa-hedral coordination environment consisting of 5 carbonyl ligands and one P atom from the bridging dppe ligand with the nearest W⁰ atom 5.625?(5)?Å away. The complex resides on a center of symmetry.

SUBMITTER: Drake HF

PROVIDER: S-EPMC5050759 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

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Publications

Crystal structure of (OC)5W(μ-dppe)W(CO)5.

Drake Hannah F HF Wheeler Kraig A KA Bellott Brian J BJ

Acta crystallographica. Section E, Crystallographic communications 20160905 Pt 10

The centrosymmetric title complex, [μ-ethane-1,2-diylbis(di-phenyl-phosphane)-κ2P:P']bis-[penta-carbonyl-tungsten(0)], [W2(C26H24P2)(CO)10], consists of two W(CO)5 moieties bridged by a bis-(di-phenyl-phosphan-yl)ethane (dppe) ligand. The W0 atom has a slightly distorted octa-hedral coordination environment consisting of 5 carbonyl ligands and one P atom from the bridging dppe ligand with the ne ...[more]

PMID: 27746924

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Project description:The salt [K(18-crown-6)]2[Ru(CN)2(CO)3] ([K(18-crown-6)]2[1]) was generated by the reaction of Ru(C2H4)(CO)4 with [K(18-crown-6)]CN. An initial thermal reaction gives [Ru(CN)(CO)4]-, which, upon ultraviolet (UV) irradiation, reacts with a second equiv of CN-. Protonation of [1]2- gave [HRu(CN)2(CO)3]- ([H1]-), which was isolated as a single isomer with mutually trans cyanide ligands. The complex cis,cis,cis-[Ru(pdt)(CN)2(CO)2]2- ([2]2-) was prepared by the UV-induced reaction of [1]2- with propanedithiol (pdtH2). The corresponding iron complex cis,cis,cis-[Fe(pdt)(CN)2(CO)2]2- ([3]2-) was prepared similarly. The pdt complexes [2]2- and [3]2- were treated with Fe(benzylideneacetone)(CO)3 to give, respectively, [RuFe (μ-pdt)(CN)2(CO)4]2- ([5]2-) and [Fe2(μ-pdt)(CN)2(CO)4]2- ([4]2-). The pathway from [3]2- to Fe2 complex [4]2- implicates intermetallic migration of CN-. In contrast, the formation of [5]2- leaves the Ru(CN)2(CO) center intact, as confirmed by X-ray crystallography. The structure of [5]2- features a "rotated" square-pyramidal Fe(CO)2(μ-CO) site. NMR measurements indicate that the octahedral Ru site is stereochemically rigid, whereas the Fe site dynamically undergoes turnstile rotation. 57Fe Mössbauer spectral parameters are very similar for rotated [5]2- and unrotated Fe2 complex [4]2-, indicating the insensitivity of that technique to both the geometry and the oxidation state of the Fe site. According to cyclic voltammetry, [5]2- oxidizes at E1/2 ∼ -0.8 V vs Fc+/0. Electron paramagnetic resonance (EPR) measurements show that 1e- oxidation of [5]2- gives an S = 1/2 rhombic species, consistent with the formulation Ru(II)Fe(I), related to the Hox state of the [FeFe] hydrogenases. Density functional theory (DFT) studies reproduce the structure, 1H NMR shifts, and infrared (IR) spectra observed for [5]2-. Related homometallic complexes with both cyanides on a single metal are predicted to not adopt rotated structures. These data suggest that [5]2- is best described as Ru(II)Fe(0). This conclusion raises the possibility that for some reduced states of the [FeFe]-hydrogenases, the [2Fe]H site may be better described as Fe(II)Fe(0) than Fe(I)Fe(I).

Project description:The cobalt carbonate hydroxide Co2CO3(OH)2 is a technologically important solid which is used as a precursor for the synthesis of cobalt oxides in a wide range of applications. It also has relevance as a potential immobilizer of the toxic element cobalt in the natural environment, but its detailed crystal structure is so far unknown. The structure of Co2CO3(OH)2 has now been investigated using density functional theory (DFT) simulations and powder X-ray diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. Two possible monoclinic phases are considered, with closely related but symmetrically different crystal structures, based on those of the minerals malachite [Cu2CO3(OH)2] and rosasite [Cu1.5Zn0.5CO3(OH)2], as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite [Cu1.34Co0.66CO3(OH)2]. The DFT simulations predict that the rosasite-like and malachite-like phases are two different local minima of the potential energy landscape for Co2CO3(OH)2 and are practically degenerate in energy, while the orthorhombic and triclinic structures are unstable and experience barrierless transformations to the malachite phase upon relaxation. The best fit to the PXRD data is obtained using a rosasite model [monoclinic with space group P1121/n and cell parameters a = 3.1408 (4) Å, b = 12.2914 (17) Å, c = 9.3311 (16) Å and γ = 82.299 (16)°]. However, some features of the PXRD pattern are still not well accounted for by this refinement and the residual parameters are relatively poor. The relationship between the rosasite and malachite phases of Co2CO3(OH)2 is discussed and it is shown that they can be seen as polytypes. Based on the similar calculated stabilities of these two polytypes, it is speculated that some level of stacking disorder could account for the poor fit of the PXRD data. The possibility that Co2CO3(OH)2 could crystallize, under different growth conditions, as either rosasite or malachite, or even as a stacking-disordered phase intermediate between the two, requires further investigation.

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Crystal structure of (OC)₅W(?-dppe)W(CO)₅.

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Crystal structure of (OC)<sub>5</sub>W(μ-dppe)W(CO)<sub>5</sub>.

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Crystal structure of (OC)5W(?-dppe)W(CO)5.

Publications

Crystal structure of (OC)<sub>5</sub>W(μ-dppe)W(CO)<sub>5</sub>.

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OmicsDI is part of the ELIXIR infrastructure

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Crystal structure of (OC)₅W(?-dppe)W(CO)₅.