Abstract The complexation reaction of copper(II) ion and N-(m-hydroxyphenylene)salicylideneaminate (mhsa) in EtOH yields EtOH-inclusion and noninclusion crystalline samples, [Cu(mhsa)2]·2EtOH (1) and [Cu(mhsa)2] (2), respectively. The amorphous sample obtained by drying 1 rearranges to the noninclusion complex 2 under alcohol vapor in the solid state.
Reaction of Mo(S(t)Bu)(4) with 2 equiv of HSCH(2)CH(2)PMe(2) (Hdmsp) produced Mo(dmsp)(2)(S(t)Bu)(2) (1) in high yield. Treatment of 1 with FeCl(2) and CuBr led to the formation of heterometallic clusters, [Mo(O)(dmsp)(2)](2)FeCl(2) (2) and [MoBr(dmsp)(2)(&mgr;(3)-S)Cu(2)](2)(&mgr;(2)-S(t)Bu)(2) (3), respectively. The structures of 1-3 were determined by X-ray analyses. Complex 1 assumes a distorted octahedral geometry with a cis-disposition of two (t)BuS ligands. In the structure of 2, an FeCl(2) unit bridges two square-pyramidal Mo(O)(dmsp)(2) fragments through interactions between Fe and dmsp sulfur atoms, where the MoS(2)Fe quadrilateral is puckered. Formation of 3 involves C-S bond cleavage of one (t)BuS ligand of 1 and rearrangement of ligands between the Mo and Cu coordination sites, resulting in the structure consisting of two MoCu(2)BrS(dmsp)(2) cluster units and two (t)BuS bridges.
Here we show that a tridentate bis(aryloxide)anilide-ligated titanium/potassium scaffold promotes functionalization of coordinated N2 with CO2 and CS2 through formation of N-C bonds. Treatment of a naphthalene complex with N2 gave an end-on bridging dinitrogen complex featuring a [Ti2 K2 N2 ] core. The dinitrogen complex underwent insertion of CO2 into each Ti-NN bond to afford an N,N'-dicarboxylated hydrazido complex. Stepwise nitrogen-carbon bond formation at coordinated N2 proceeded to afford an unsymmetric hydrazido complex upon sequentially treating the dinitrogen complex with CS2 and CO2 . Addition of Me3 SiCl to the dicarboxylated hydrazido complex resulted in partial silylation of the carboxylate groups but did not lead to removal of the functionalized N2 unit from the metal centers. However, reduction of the dicarboxylated hydrazido complex with potassium naphthalenide afforded an oxo-bridged dinuclear complex along with release of free potassium cyanate.
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An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
