The application of solvent-assisted mechanochemical synthesis to the study of metal complex formation is illustrated by examples involving complexes of silver halides with ethylenethiourea.

Several synthetic strategies using copper(I) starting materials or copper(II) compounds and an in situ sulfite reductant have been used to systematically explore the chemistry of copper(I) complexes with thiourea and substituted thiourea ligands. This has resulted in the discovery of several new complexes and methods for the bulk synthesis of some previously reported complexes that had been prepared adventitiously in small quantity. The new complexes are (tu = thiourea, dmtu = N,N'-dimethylthiourea, etu = ethylenethiourea): [I(4)Cu(4)(tu)(6)].H(2)O, [Cu(4)(tu)(10)](NO(3)).tu.3H(2)O, [BrCu(dmtu)(3)], [ICu(dmtu)(3)](2), [BrCu(etu)(2)](2), [ICu(etu)(2)], [ICu(etu)(2)](3). [I(4)Cu(4)(tu)(6)].H(2)O has an adamantanoid structure, with four terminal iodide ligands and six doubly bridging tu ligands. In contrast to this, [Cu(4)(tu)(10)](NO(3)).tu.3H(2)O contains a tetranuclear cluster in which four of the tu ligands are terminal and the other six are doubly bridging. [BrCu(dmtu)(3)] is a mononuclear complex with tetrahedral coordination of copper by one bromide and three dmtu ligands, whereas [Cu(dmtu)(3)](2)I(2) has a centrosymmetric dimeric cation with two uncoordinated iodides, four terminal dmtu and two doubly bridging dmtu ligands, [(dmtu)(2)Cu(mu-S-dmtu)(2)Cu(dmtu)(2)]I(2). A reversal of this monomer to dimer trend from bromide to iodide is seen for the etu counterparts: [BrCu(etu)(2)](2) is a centrosymmetric dimer with two doubly bridging etu ligands, [(etu)BrCu(mu-S-etu)(2)CuBr(etu)], whereas [ICu(etu)(2)] is a trigonal planar monomer, although the novel [I(3)Cu(3)(etu)(6)] is also defined. Infrared and Raman spectra of the synthesized complexes were recorded and the metal-ligand vibrational frequencies have been assigned in many cases. The results confirm previously observed correlations between the vibrational frequencies and the corresponding bond lengths for complexes of the unsubstituted tu ligand. A mechanochemical/infrared method was used to synthesize [I(3)Cu(3)(etu)(6)] from CuI and etu, and to demonstrate the polymorphic transition from [ICu(etu)(2)] to [I(3)Cu(3)(etu)(6)].

Singlecrystal X-ray diffract ion structure determi nations, high resolution solid -state crosspolarization magic-angle spinning 31P n.m.r., and far4.r. spectral data are reported for the mononuclear 2 : 1 adducts of triphenylphosphine with copper( I) and gold( I ) halides, [ M (PPh,),X] .

Recrystallization of [Cu,l,( PPh,),] from toluene has yielded a new polymorph of that compound, (1 ), which has been shown by single-crystal X-ray diffraction analysis to have a tetrametallic 'cubane' structure rather than the expected 'step' structure. Crystals are monoclinic, space group P2,/n, with a = 19.47( 1 ), b = 26.94(1), c = 13.528(5) A, p = 98.98(4)", Z = 4 tetramers; R was 0.06 for No =

Three new 10-membered macrolides (1-3) have been isolated from the entomopathogenic fungus Cordyceps militaris BCC 2816, together with six known compounds, cepharosporolides C (4), E (5), and F (6), 2-carboxymethyl-4-(3'-hydroxybutyl)furan (7), cordycepin (8), and pyridine-2,6-dicarboxylic acid. The structures were determined by analysis of NMR data, and an X-ray analysis was performed to confirm the structure of 1. The antimalarial activity of 1-4 and 8 against Plasmodium falciparum K1 was evaluated.

The crystal structures of the title compounds have been determined by single-crystal X-ray diffraction methods at 295 K, and refined by least-squares methods. Crystal data for [Cu(Cl4H12N2)2] Br.H2O (1) are: monoclinic, P21/c, a 14.067(4), b 17.687(6), c 10.337(5) �, β 91.04(3)�, with R 0.038, R' 0.040 for 1855 'observed' reflections. Crystal data for [Cu(Cu14H12N2)2] C1.2H2O (2) are: triclinic, P1, a 15.305(2), b 13.164(2), c 7.344(3) �, α 83.03(3), β 93.83(3), γ 108. 11260(3)�, with R 0.051, R' 0.053 for 1293 'observed' reflections. Crystal data for [Cu(Cl4H12N2)2] Br.H2O (3) are: triclinic, P1, a 7.619(2), b 11.967(3), c 15.534(3) �, α 71.26(1), β 82.13(1), γ 86.86(2)�, with R 0.043, R' 0.052 for 2335 'observed' reflections. The anionic and solvent species are uncoordinated in all three compounds. Cu-N bond lengths range from 2.027(5) to 2.053(5) �. The copper(1) environment (CuN4) in each complex shows considerable distortion from tetrahedral geometry. N-Cu-N intraligand angles range from 81.0(2) to 83.0(2)�, while N-Cu-N interligand angles range from 114.7(2) to 135.2(2)�. The variation in interligand angles can be described in terms of three independent rotations of ligand 2 about an orthogonal axial system defined by ligand 1.

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Two new hirsutane sesquiterpenes, connatusins A (1) and B (2), were isolated from the fungus Lentinus connatus BCC 8996. The structures, closely related to hypnophilin, were elucidated on the basis of the spectroscopic data. An X-ray analysis was performed to confirm the structure of 1. Six known compounds were also obtained. Panepoxydone (5), panepoxydione (6), and dihydrohypnophilin (8) exhibited significant antimalarial and cytotoxic activities.