Thermolysis of nido-[(Cp*Mo)2B4TeClH 5], with an excess of Co2(CO)8 at room temperature, afforded a triple-decker sandwich complex [(Cp*Mo) 2{μ-η6:η6-B3H 3TeCo2(CO)5}] (4), which represents an unsaturated 24-valence-electron sandwich cluster in which the middle deck is composed of B, Co, and a heavy group 16 element. © 2013 American Chemical Society.

Sundargopal Ghosh

Department Of Chemistry

Bijan Mondal

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

Inorganic Chemistry

We report the synthesis, isolation and structural characterization of several crystalline, moderately air stable nido-metallaboranes which represent novel metal rich open cage systems.The reaction of [Cp*CoCl]2, (Cp* = ν5-C5Me5), with [LiBH 4·thf] in toluene at-78 °C, followed by thermolysis with [BH3·thf] in boiling toluene yielded clusters, [(Cp*Co)3B6H8O] (1) and [(Cp*Co)2B8H11Me] (2). Under the similar reaction condition, [Cp*RhCl2]2 yielded [(Cp*Rh)3B7H11] (3) and [(Cp*Rh)2B8H12] (4). All the new compounds, 1-4 have been characterized by elemental analysis, IR, 1H, 11B, 13C NMR spectroscopy, and the geometric structures were unequivocally established byX-ray diffraction analysis of compound 1-4. Quantum chemical calculation by using density functional theory method is implemented on model compounds 10-40 (10-40 are the Cp analogs of 1-4 respectively, Cp = C5H5) and yields geometries in agreement with the X-ray detaermined geometries. Large HOMO-LUMO gaps are in tally with the higher stabilities of 10 and 30. © The National Academy of Sciences, India 2014.

Proceedings of the National Academy of Sciences India Section A - Physical Sciences

Synthesis, characterization and electronic structures of Rh and co analogs of decaborane-14

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

Density functional theory (DFT) has been used to probe the bonding and electronic properties of dimolybdaborane [(Cp*Mo)2B 5H9], 1 (Cp* = η5-C 5Me5), and several other heterodimolybdaborane clusters, such as [(Cp*Mo)2B5(μ3-OEt)H 7] (2), [(Cp*Mo)2B5(μ3-OEt) (n-BuO)H6] (3), [(η5-C5H5W) 2B4H4S2] (4), and [(Cp*Mo)2B4H4E2] (5-7, where, for 5, E = S, for 6, E = Se, and for 7, E = Te). The DFT results were also used to address some key points such as (i) the metal-metal bond length, (ii) the location and number of bridging and terminal hydrogen atoms, (iii) the molecular orbital analysis, and (iv) the assignment of 11B and 1H NMR chemical shifts. These studies further provide meticulous insight into similarities and differences between various dimetallaborane clusters 1-7. In addition, the crystal structures of 5 and 7 are reported, which come on top of the already existing literature of dimetallaboranes and support the theoretical findings. © 2012 American Chemical Society.

Journal	Inorganic Chemistry
ISSN	00201669
Open Access	No