The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizi...

Cyclic polyamine 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane, (Me(3)TACD)H (= Me(3)[12]aneN(4)), reacted with [K{N(SiHMe(2))(2)}] in benzene-d(6) to give [K{(Me(3)TACD)SiMe(2)N(SiHMe(2))}] (1) under hydrogen evolution. Single-crystal X-ray diffraction of 1 shows a dinuclear structure in the solid state, featuring a bridging μ-amido and a weak β-agostic Si-H bond. 1,7-Dimethyl-1,4,7,10-tetraa...

The synthesis and characterisation of several sodium zincate complexes are reported. The all-alkyl monomeric sodium zincate, (PMEDTA)·Na(μ-CH2SiMe3)Zn(t)Bu22, is prepared by combining equimolar quantities of (t)Bu2Zn, (n)BuNa and PMDETA (N,N,N',N'',N''-pentamethyldiethylenetriamine)]. A similar approach was used to prepare and isolate the unusual dimeric zincate [(PMEDTA)·Na(μ-(n)Bu)Zn(t)Bu2]23...

In the title compound, [Zn(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)](n), the Zn(II) ion is tetrahedrally coordinated by two formyl-benzoate (FB) and one isonicotinamide (INA) ligands while symmetry-related FB ligands bridge adjacent Zn(II) ions, forming polymeric chains along the b axis. The carboxyl-ate groups in the two FB ions are twisted away from the attached benzene ring by 9.07 (2) and 26.2 (2)°....

The terphenyl structure has been proven to be an ideal scaffold mimicking side-chain functionalities of peptidic alpha-helices. The synthesis of 1,4-dipiperazino benzenes, using stepwise transition metal-catalyzed N-arylation of chiral piperazines to a central benzene core is reported. The structure determination by X-ray crystallography reveals a geometrical arrangement of the hydrophobic side...

The photostability of various electro-optic active guest–host polymers, doped with chromophores that possess very efficient cyano-containing acceptors and dialkyaminoor diarylamino-benzenes, and also their extended thiophene analogs as bridging structures, has been investigated over a broad wavelength range in the near infrared and the visible. A variation of over 2 orders of magnitude was foun...

Various new thermally air- and water-stable alkyl and aryl analogues of (acac-O,O)2Ir(R)(L), R-Ir-L (acac-O,O = kappa2-O,O-acetylacetonate, -Ir- is the trans-(acac-O,O)2Ir(III) motif, R = CH3, C2H5, Ph, PhCH2CH2, L = Py) have been synthesized using the dinuclear complex [Ir(mu-acac-O,O,C3)-(acac-O,O)(acac-C3)]2, [acac-C-Ir]2, or acac-C-Ir-H2O. The dinuclear Ir (III) complexes, [Ir(mu-acac-O,O,C...

In the title complex, [Mn(C(8)H(4)O(7)S)(C(12)H(8)N(2))(2)], the Mn(II) atom is chelated by one 4-carb-oxy-2-sulfonato-benzoate anion and two phenathroline (phen) ligands in a distorted octa-hedral MnN(4)O(2) geometry. The benzene ring of the 4-carb-oxy-2-sulfonato-benzoate anion is twisted with respect to the two phen ring systems at dihedral angles of 66.38 (9) and 53.56 (9)°. In the crystal,...

The crystal structure of the title compound 3CP4MBA, C(14)H(11)ClO(2), resembles those of 3-methyl-phenyl 4-methyl-benzoate (3MP4MBA), 4-methyl-phenyl 4-methyl-benzoate (4MP4MBA), 4-methyl-phenyl 4-chloro-benzoate (4CP4MBA) and other aryl benzoates with similar bond parameters. The dihedral angle between the benzene rings in 3CP4MBA is 71.75 (7)°, compared with 56.82 (7)° in 3MP4MBA and 63.57 (...

In the title salt {systematic name: 1-[(1,3-benzodioxol-5-yl)meth-yl]piperazin-1-ium 4-chloro-benzoate}, C12H17N2O2 (+)·C7H4ClO2 (-), the piperazine ring adopts a slightly disordered chair conformation. The dioxole ring is in a flattened envelope conformation with the methyl-ene C atom forming the flap. The relative orientation of the piperonyl ring system and the piperazine rings is reflected ...