Pyrolysis of an in-situ generated intermediate, produced in the reaction of [CpMoCl4], 1, (Cp= η5-C5Me5) with [LiBH4·THF], with an excess of difuryl ditelluride in toluene at 90 °C yielded syn and anti isomers of [CpMo(O)(μ-Te)] 2 (2, 3) and [Cp2Mo2O2(μ-O)(μ- Te)] (4, 5). In a similar fashion, dibenzyl diselenide yielded syn and anti isomers of [CpMo(O)(μ-Se)]2 (6, 7), along with the known nido-[(CpMo)2B4H8Se2]. Note that in parallel with 2-7, [(CpMo)2B5H9] was isolated as the major product in both cases. Compounds 2-7 have been isolated in modest yield as orange to brown crystalline solids. All the new compounds have been characterized in solution by mass, IR, 1H, 13C, 77Se and 125Te NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of 2-4 and 7. © 2011 Elsevier Ltd. All rights reserved.

Sundargopal Ghosh

Department Of Chemistry

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Polyhedron

Recently we described the synthesis and structural characterization of various dimetallaherteroborane clusters, namely nido-[(Cp∗Mo)2B4ECl x H6-x ], 1-3; (1: E = S, x = 0; 2: E = Se, x = 0; 3: E = Te, x = 1). A combined theoretical and experimental study was also performed, which demonstrated that the clusters 1-3 with their open face are excellent precursors for cluster growth reaction. In this investigation process on the reactivity of dimetallaheteroboranes with metal carbonyls, in addition to [(Cp∗Mo)2B4H6EFe(CO)3] (4: E = S, 6: E = Te) reported earlier, reaction of 2 with [ Fe2(CO)9] yielded mixed-metallaselenaborane [(Cp∗Mo)2B4H6SeFe(CO)3], 5 in good yield. The quantum chemical calculation using DFT method has been carried out to probe the bonding, NMR chemical shifts and electronic properties of dimolybdaheteroborane clusters 4-6. [Figure not available: see fulltext.] © 2014 Indian Academy of Sciences.

Fulltext

Journal of Chemical Sciences

Dimetallaheteroborane clusters containing group 16 elements: A combined experimental and theoretical study

Chemistry and reactivity of dimolybdathiaborane, [(Cp*Mo) 2B2SH2], 1, obtained from the reaction of 2-mercaptobenzothiazole, [Cp*MoCl2] and [LiBH2.thf], has been explored with dinuclear metal carbonyl [Fe2(CO) 2]. As a result, reaction of 1 with [Fe2(CO)2] yielded heterometallathiaborane, [(Cp*Mo)2B2H 2SFe(CO)2], 2 in good yield. Both the new compounds have been characterized in solution by 1H, 11B and 13C NMR spectroscopy and the structural types were unequivocally established by X-ray crystallographic analysis of compound 2. Cluster 2 has a bicapped octahedral geometry with the {Fe(CO)3} fragment occupying one of the high-connectivity cluster vertexes rather than a capping position. Interestingly, cluster 1 undergoes geometric changes (bicapped trigonal bipyramid → bicapped octahedron) on the addition of two-electron {Fe(CO)3} fragment to 1. © Indian Academy of Sciences.

Journal	Polyhedron
ISSN	02775387
Open Access	No