Treatment of group 5 metal polychlorides such as, [Cp nMCl 4-x] (M = V: n, x = 2; M = Nb: n = 1, x = 0), or [CpTaCl 4] (Cp = η 5-C 5H 5, Cp = η 5- C 5Me 5), with [LiBH 4·THF] followed by thermolysis in the presence of diphenyl diselenide yielded metallaheteroborane clusters [{CpV(μ-SePh)} 2(μ-Se)], 1 [(CpNb) 2B 4H 9(μ-SePh)], 2 and [(CpTa) 2B 4H 11(SePh)], 3 in modest yields. Compound 1 is an organovanadium selenolato cluster in which two (CpV) moieties bridged by (μ-Se) and two (μ-SePh) ligands. Compound 2 exhibits a bicapped tetrahedral core with one (μ-SePh) ligand. 3 is a tantalahexaborane cluster in which one of the terminal BH protons is substituted by SePh. Compounds 1-3 have been characterized by mass spectrometry, 1H, 11B, 13C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis of 1-3. © 2011 Elsevier B.V. All rights reserved.

Sundargopal Ghosh

Department Of Chemistry

Chalcogens

CRYSTALLOGRAPHIC ANALYSIS

DIPHENYL DISELENIDE

GEOMETRIC STRUCTURE

Metallaboranes

Ligands

Mass spectrometry

Niobium

Nuclear magnetic resonance spectroscopy

selenium

Selenium compounds

Transition metals

Vanadium Compounds

Fulltext

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IIT Madras

Journal of Organometallic Chemistry

Metal-rich metallaboranes: An exo-Fe(CO)3 moiety linked to a cubane core is the most prominent feature of complexes [(Cp*M) 2(μ3-E)2B2H(μ-H){Fe(CO) 2}2Fe(CO)3] (M=Mo, E=S, Se; M=Ru, E=CO; Cp*=n5-C5Me5), which are the first heterobimetallic cubane-type clusters with a boride unit (see structure). © 2011 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Angewandte Chemie - International Edition

A family of heterometallic cubane-type clusters with an exo-Fe(CO) 3 fragment anchored to the cubane

Vanadaborane, [(CpV)2(B2H6)2] (Cp = η5-C5H5), 1 reacts with elemental sulfur to afford the hexasulflde cluster [(CpV)2S4(μ- η1-S2)], 2 In high yield. Compound 2 is a notable example of an organovanadium sulfide cluster In which the [V2S 4] atoms define a bicapped tetrahedron framework, with μ-η1-S2 ligand bridged the two (CpV) moieties. The sulfur atom In [V2S4] core in 2 Is a four-skeletal- electron donor isoelectronlc with the BH3 unit; therefore, the replacement of boron hydride in 1 by four sulfur atoms necessitates the formation of a bicapped tetrahedron [V2S4] framework. Furthermore, this Is the only reported example of a bimetallic hexasulflde cluster containing vanadium. Pyrolysls of 1 with bis-chalcogenide ligands such as Ph2S2 and Bz2Se2 (Bz = PhCH 2), results In the formation of substituted vanadahexaboranes [(CpV)2B4H12-xLx], 3-5 (3: L = SPh: x= 3; 4: L = SPh, x= 2; 5: L = SeBz: x= 1) in modest yield. All these new compounds have been characterized by mass, 1H, 11B, 13C NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of compounds 2-5. © 2010 American Chemical Society.

Inorganic Chemistry

Chemistry of vanadaboranes: Synthesis, structures, and characterization of organovanadium sulfide clusters with disulfido linkage

Reaction of [1,2-(Cp*RuH)2B3H 7](1;Cp* = η-C5Me5) with [Mo(CO) 3(CH3CN)3] yielded arachno-[(Cp*RuCO) 2B2H6](2), which exhibits a butterfly structure, reminiscent of 7 sep B4H10. Compound 2 was found to be a very good precursor for the generation of bridged borylene species. Mild pyrolysis of 2 with [Fe2(CO)9] yielded a triply bridged heterotrinuclear borylene complex [(μ3-BH) (Cp*RuCO)2(μ-CO){Fe(CO)3}] (3) and bis-borylene complexes [{(μ3-BH)-(Cp*Ru)(μ-CO)}2Fe 2(CO)5](4) and [{(μ3-BH)(Cp*Ru)Fe(CO) 3}2(μ-CO)] (5). In a similar fashion, pyrolysis of 2 with [Mn2(CO)10] permits the isolation of μ3-borylene complex [(μ3-BH)-(Cp*RuCO) 2(μ-H)(μ-CO){Mn(CO)3}] (6) . Both compounds 3 and 6 have a trigonal-pyramidal geometry with the μ3-BH ligand occupying the apical vertex, whereas 4 and 5 can be viewed as bicapped tetrahedra, with two μ3-borylene ligands occupying the capping position. The synthesis of tantalum borylene complex [(μ3-BH)(Cp*TaCO) 2(μ-CO){Fe(CO)3}] (7) was achieved by the reaction of [(Cp*Ta)2B4H8(μ-BH4)] at ambient temperature with [Fe2(CO)9]. Compounds 2-7 have been isolated in modest yield as yellow to red crystalline solids. All the new compounds have been characterized in solution by mass spectrometry; IR spectroscopy; and 1H, 11B, and 13C NMR spectroscopy and the structural types were unequivocally established by crystallographic analysis of 2-6. © 2010 Wiley-VCH Verlag GmbH &amp; Co. KGaA.

Chemistry - A European Journal

From metallaborane to borylene complexes: Syntheses and structures of triply bridged ruthenium and tantalum borylene complexes

Reaction of {η5 -C5Me5)MoCl 4 with a 10-fold excess of LiBH4 followed by thermolysis with excess BH3·THF in toluene led to the formation of two oxamolybdaborane clusters, (η5-C5Me 5Mo)2B5(μ3OEt)H6R (2, R = H; 3, R = n-BuO). Clusters 2 and 3 have been characterized by 1H, 11B, and 13C NMR spectra and X-ray crystal structure determinations. 2 and 3 are notable examples of oxametallaborane compounds where oxygen is contiguously bound to both the cluster metal (molybdenum) and the boron atom. © 2009 American Chemical Society..

Organometallics

Unusual open eight-vertex oxamolybdaboranes: Structural characterizations of (η5-C5Me5Mo)2B 5(μ-OEt)H6R (R = H and n-BuO)

Reaction of [(η5-C5Me5)MCl4], 1-2 (1: M = Mo and 2: W) with six fold excess of [LiBH4·thf] followed by thermolysis with excess chalcogen powders (S, Se and Te) yielded dichalcomolybda- and tungstaboranes, [(η5-C5Me5M)2B4H4E2], 5-8 (5: M = Mo, E = S; 6: M = Mo, E = Se; 7: M = Mo, E = Te; 8: M = W, E = Se) in modest yields. The geometry of 5-8 resembles a hexagonal bipyramid with a missing connectivity of two chalcogen vertices and a very short cross cage metal-metal bonding. All these new dichalcometallaboranes have been characterized by mass, 1H, 11B, 13C NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of compound 6. © 2009 Elsevier B.V. All rights reserved.

Direct insertion of sulfur, selenium and tellurium atoms into metallaborane cages using chalcogen powders

Metallaheteroborane clusters of group 5 transition metals derived from dichalcogenide ligands

Journal	Journal of Organometallic Chemistry
ISSN	0022328X
Open Access	Yes