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New methylsulfate complex (Bu4N)2[Мо6I8(O3SOCH3)6] (I) is synthesized by the reaction of (Bu4N)2[Mo6I8(C≡C–C(O)OCH3)6] with dimethyl sulfate (CH3)2SO4. According to the XRD data, the molybdenum atoms are coordinated by the monodentate methylsulfate ligands. In a DMSO solution, the complex undergoes solvolysis accompanied by the complete substitution of the methylsulfate ligands by the solvent molecules. A powder sample of cluster I luminesces (phosphorescence) with the emission maximum at a wavelength of 620 nm (77 K). Increasing temperature to 300 K results in the shift of the emission maximum to 650 nm and a decrease in the integral intensity by 1.6 times. [ABSTRACT FROM AUTHOR]

Methylation of cyanide ligands in the composition of (Bu4N)4[Nb6Cl12(CN)6] and (Bu4N)4[Ta6I12(CN)6] clusters with methyl triflate CF3SO3CН3 results in the formation of respective [M6X12(CNCН3)6]2+ isonitrile complexes. They are isolated and structurally characterized in the form of triflate salts: [Nb6Cl12(CNCН3)6](CF3SO3)2 (1) and [Ta6I12(CNCН3)6](CF3SO3)2·0.86CH2Cl2 (2). [ABSTRACT FROM AUTHOR]

Two new luminescent cluster complexes (Bu4N)2[Mo6X8(N3C2H2)6]·n(H2O) (1) (X = Br, n = 4) and (2) (X = I, n = 5) are obtained by the reaction of (Bu4N)2[Mo6X8(OOCCH3)6] (X = Br, I) with 1-trimethylsilyl-1,2,4-triazole Me3Si–N3C2H2. Their crystal structures are determined and the luminescent properties of powder samples are studied. According to single crystal X-ray diffraction data, molybdenum atoms are monodentate coordinated by N1 atoms of triazolate ligands at Mo–N distances of 2.154(9)-2.185(9) Å (1) and 2.158(13)-2.21(13) Å (2). The complexes are characterized by electrospray mass spectrometry, proton magnetic resonance, elemental analysis, and IR spectroscopy data. [ABSTRACT FROM AUTHOR]

Extracting the reaction product of Ta, Br2, and LiBr (720 °C, 48 h, mole ratio 1.5:1.75:1.0) with diglyme yields crystals of complex [Li(diglyme)2]2[Ta6Br18] whose structure is determined by XRD. [ABSTRACT FROM AUTHOR]

Two new cluster complexes (Bu4N)2[Mo6X8(OOC–C≡CH)6] (1) (X = Br) and (2) (X = I) are synthesized by the reaction of (Bu4N)2[Mo6X8(OOCCH3)6] (X = Br, I) with HOOC–C≡CH propiolic acid, their crystal structures are determined, and the luminescent properties are studied for powder samples at different temperatures. According to X-ray crystallographic data, molybdenum atoms are monodentately coordinated by oxygen atoms of the carboxyl group at Mo–O distances of 2.108(2)-2.121(16) Å. The propiolate complexes are characterized by electrospray mass spectrometry, 1Н and 13С NMR, elemental analysis, and IR spectroscopy. [ABSTRACT FROM AUTHOR]

The first iodide cluster of molybdenum with the metal cage in the form of a tetragonal pyramid (Bu4N)[Mo5OI13]·THF (I) and cocrystallizate (Bu4N){[Mo5OI13]0.9[Mo6I14]·THF (II) are synthesized for the first time by heating a LiI–I2–Mo mixture in a temperature range of 300–400°С followed by the extraction of the product. Complexes I and II are studied by X-ray diffraction analysis (CIF files CCDC nos. 2063029 (I) and 2063030 (II)). The molybdenum atoms in [Mo5OI13]– form a square pyramid with Mo–Mo distances of 2.67 Å between the basal molybdenum atoms and the Mo–Mo distances equal to 2.72 Å between the apical and basal molybdenum atoms. The oxygen atom is coordinated to the pyramid base (Mo–μ4-O 2.10 Å). The cluster anion [Mo5OI13]– can be presented as the octahedral cluster anion [Mo6I14]2– in which the position of the {MoI}– fragment (d0, 6e) is occupied by the isoelectronic oxygen atom (s2p4, 6e). In the structure of compound II, the [Mo5OI13]– and [Mo6I14]2– cluster anions occupy close atomic positions. [ABSTRACT FROM AUTHOR]

The reaction of Re3Br9 with P(CH2OH)3 (THP) in methanol under inert atmosphere gives a new cluster complex, [Re3(µ2‑Br)3Br3(µ3-P,O,O-P(CH2OH)(CH2O)2)2H] ∙ 0.8H2O · 1.6MeOH (I). With access of air, the reaction produces a different product, [{Re3(µ2-Br)3Br2(OCH2)2PCH2-OP(CH2OH)2}2-{(P(CH2OH)(CH2O)2)}2] (II), in which two triangular clusters are linked by deprotonated THP molecules as bridging ligands. In addition, each cluster is coordinated in a tetradentate fashion by the phosphine-phosphinite ligand, resulting from the oxidative condensation of two THP molecules (CIF files CCDC 1829565 (I) and 1829566 (II)). [ABSTRACT FROM AUTHOR]

The crystal structure of [(C5Me4Et)3Rh3(μ3-Se)2](PF6)2 and [(C5Me4Et)2Rh2(μ2-Cl)3]PF6, obtained in the reaction of [(C5Me4Et)Rh(C6H6)](PF6)2 with ZnSe in 4M HCl under hydrothermal conditions, is determined. In agreement with the 18VE rule, the triangular cluster contains single metal-metal bonds (Rh-Rh 2.864(1) Å), whereas they are absent in the binuclear complex (Rh ...Rh 3,216(1) Å). [ABSTRACT FROM AUTHOR]

Various synthetic approaches are used to obtain new triangular complexes with rare cluster nuclei M3Te7 (M = Mo, W), as well as with partial substitution for chalcogen W4+ (M = Mo, W), as well as with partial substitution for chalcogen W3Te3.8Se. The crystalline structure has been identified for K5{[Mo3Te7(CN)6]2I}·2.5H2O ( I), K3{[Mo3Te7(CN)6]SeCN}·3.25H2O ( II), Cs2K{ [W3Te7(CN)6]Br0.8Cl0.2}·2.5H2O ( III), Cs3{ [W3Te7(CN)6]Br}·2H2O ( IV), Cs1.59K1.41{[W3Te3.8Se3.2× ×(CN)6]Br}·1,5H2O ( V), [W3Te7((EtO)2PS2)3]Br ( VI). The compounds are characterized by IR methods and electronic spectroscopy, electrospray-mass-spectrometry. The crystalline structure of this class of compounds is analyzed. Specific non-valence interactions in these systems are considered in detail. [ABSTRACT FROM AUTHOR]

Methylation of cyanide ligands in the composition of (Bu4N)4[Nb6Cl12(CN)6] and (Bu4N)4[Ta6I12(CN)6] clusters with methyl triflate CF3SO3CН3 results in the formation of respective [M6X12(CNCН3)6]2+ isonitrile complexes. They are isolated and structurally characterized in the form of triflate salts: [Nb6Cl12(CNCН3)6](CF3SO3)2 (1) and [Ta6I12(CNCН3)6](CF3SO3)2·0.86CH2Cl2 (2). [ABSTRACT FROM AUTHOR]

Extracting the reaction product of Ta, Br2, and LiBr (720 °C, 48 h, mole ratio 1.5:1.75:1.0) with diglyme yields crystals of complex [Li(diglyme)2]2[Ta6Br18] whose structure is determined by XRD. [ABSTRACT FROM AUTHOR]