Dicarbonyl­dichlorido(N,N,N′,N′-tetra­methyl­ethylenediamine)­ruthenium(II)

In the title compound, [RuCl2(C6H16N2)(CO)2], the geometry around the RuII atom is a distorted RuC2N2Cl2 octa­hedron, with pairs of C and Cl atoms trans to each other and the N atoms of the bidentate ligand in a cis conformation. The five-membered chelate ring is puckered on the C—C bond

Water-stable zirconium-based metal-organic framework material with high-surface area and gas-storage capacities.

We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2) g(-1) ; to our knowledge, currently the highest published for Zr-based MOFs. CH4 /CO2 /H2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g(-1) , which corresponds to 43 g L(-1) . The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 vSTP /v and 0.27 g g(-1) , respectively.OKF, JTH and RQS thank DOE ARPA-E and the Stanford Global Climate and Energy Project for support of work relevant to methane and CO2, respectively. TY acknowledges support by the U. S. Department of Energy through BES Grant No. DE-FG02-08ER46522. WB acknowledges support from the Foundation for Polish Science through the “Kolumb” Program. DFJ acknowledges the Royal Society (UK) for a University Research Fellowship. This material is based upon work supported by the National Science Foundation (grant CHE-1048773).This is the accepted manuscript. The final version is available as 'Water-Stable Zirconium-Based Metal–Organic Framework Material with High-Surface Area and Gas-Storage Capacities' from Wiley at http://onlinelibrary.wiley.com/doi/10.1002/chem.201402895/abstract

The geometry of SiOCN and SiNCO linkages. The crystal structures of (Me3Si)2(Ph2MeSi)CSiMe2OCN and (PhMe2Si)3CSiMe2NCO

Single crystal X-ray diffraction studies have been carried out on the title compounds (in the case of the cyanate as its methylcyclohexane solvate). The geometry of the SiNCO fragment in the isocyanate (PhMe2Si)2CSiMe2NCO (<SiNC = 155.7(5), <NCO = 175.9(7)°, d(Si-N) = 1.739(5), d(N-C) = 1.135(8), d(C-C) 1.174(8) Å) is very similar to that in the much less crowded compounds H3SiNCO and ClCH2Me2SiNCO, but in all three compounds the Si-N-C angle of 180° in H3SiNCO is Me3SiNCO. In the light of the results the validity of recent calculations indicating and Si-N-C angle of 180° in H3SiNCO is questioned. In the case of the cyanate (Me3Si)2(Ph2MeSi)CSiMe2OCN, disorder results in considerable uncertainty in the geometry of the SiOCN linkage, but the values for the O-C-N and Si-O-C angles, 175(1)° and ca. 124 ± 6°, respectively, are consistent with those predicted by the corresponding calculations on H3SiOCN

A versatile bulky bidentate ligand for both main group and transition metals. Derivatives of lithium potassium magnesium chromium manganese and cobalt containing the C(SiMe3)2(SiMe2C5H4N-2)

The compound HC(SiMe3)2(SiMe2C5H4N-2), 1, reacts with methyllithium in THF to give a good yield of the lithium derivative which has been isolated as a molecular THF adduct 2. This reacts (a) with KOtBu to give 3, which crystallizes in a solvent-free ionic lattice, (b) with MgBr2 to give the Grignard reagent 4, and (c) with CrCl2 to give Cr{C(SiMe3)2(SiMe2C5H4N-2)}2, 5, along with the halide-bridged Grignard reagent analogue 6, which crystallizes in a lattice containing alternate THF-free molecules (6a) and molecules (6b) with coordinated THF. The reactions of 2 with MnCl2 and CoBr2 give the halide-bridged ate complexes 7, and 8, respectively

Attachment of the New Bulky Ligand (Me3Si)2(Me2NMe2Si)C to Li Hg Al Ga and Sn. Crystal Structures of [Li\{C(SiMe3)2(SiMe2NMe2)\}(THF)2] [Hg\{C(SiMe3)2(SiMe2NMe2)\}2] [Al\{C(SiMe3)2(SiMe2NMe2)\}X2] (X=Cl Ph) and [Ga\{c(SiMe3)2(SiMe2NMe2)\}Cl2]

The organolithium reagent (1) is readily obtained by reaction of the chloride (Me3Si)2(Me2NMe2Si)CCl with LiBu in THF (tetrahydrofuran) at low temperature. Reactions of 1 with HgBr2, AlCl3, GaCl3, and SnCl4 give [Hg{C(SiMe3)2(SiMe2NMe2)}2] (2), (3), Ga{C(SiMe3)2(SiMe2NMe2)}Cl2 (5), and [Sn{C(SiMe3)2(SiMe2NMe2)}Cl3] (6), respectively, and treatment of 3 with LiPh gives (4). Crystal structure determinations have shown that there is intramolecular coordination of the N atom to the metal M, with formation of a planar four-membered ring, in 1, 3, 4, and 5 (but not 2). Engagement of the lone pair on N in coordination with Al in 3 results in an exceptionally long Si−N bond length of 1.875(2) Å, some 0.16 Å longer than that in 2 and in simple silylamines generally; the Si−N bond is possibly shorter in 4 (1.851(2) Å) and 5 (1.858(4) Å), and is markedly so in 1 (1.796(4) Å), but still notably long. The lengths of the N−metal bonds in these compounds are similar to those between alkylamines and the metals in coordination compounds, indicating that at least in these systems the N atoms in the silylamines coordinate as strongly as those in the organic amines. Reaction of 6 with MeOH occurs exclusively at the Si−N bond to give [Sn{C(SiMe3)2(SiMe2OMe)}Cl3], that of 2 with ICl or CF3CO2H gives [Hg{C(SiMe3)2(SiMe2Cl)}2] and [Hg{C(SiMe3)2(SiMe2O2CCF3)}2], respectively, and that of 1 with ICH2CH2I gives the iodide (Me3Si)2(Me2NMe2Si)CI

A versatile bulky bidentate ligand for both main group and transition metals. Derivatives of lithium potassium magnesium chromium manganese and cobalt containing the C(SiMe3)2(SiMe2C5H4N-2)

The compound HC(SiMe3)2(SiMe2C5H4N-2), 1, reacts with methyllithium in THF to give a good yield of the lithium derivative which has been isolated as a molecular THF adduct 2. This reacts (a) with KOtBu to give 3, which crystallizes in a solvent-free ionic lattice, (b) with MgBr2 to give the Grignard reagent 4, and (c) with CrCl2 to give Cr{C(SiMe3)2(SiMe2C5H4N-2)}2, 5, along with the halide-bridged Grignard reagent analogue 6, which crystallizes in a lattice containing alternate THF-free molecules (6a) and molecules (6b) with coordinated THF. The reactions of 2 with MnCl2 and CoBr2 give the halide-bridged ate complexes 7, and 8, respectively

Selective Solvent-Assisted Linker Exchange (SALE) in a Series of Zeolitic Imidazolate Frameworks

Solvent-assisted linker exchange (SALE) has recently emerged as an attractive strategy for the synthesis of metal–organic frameworks (MOFs) that are unobtainable via traditional synthetic pathways. Herein we present the first example of selective SALE in which only the benzimiadazolate-containing linkers in a series of mixed-linker zeolitic imidazolate frameworks (ZIF-69, -78, and -76) are replaced. The resultant materials (SALEM-10, SALEM-10b, and SALEM-11, respectively) are isostructural to the parent framework and in each case contain trifluoromethyl moieties. We therefore evaluated each of these materials for their hydrophobicity in condensed and gas phases. We expect that selective SALE will significantly facilitate the design of improved, and potentially complex, MOF materials with new and unusual properties