IFCPAR AR (ENGLISH) for CD - CEFIPRA

CEFIPRA
Centre Franco-Indien pour la Promotion de la Recherche Avancée
Duration: Three years (February, 2011 to January, 2014)
Objectives
While carbon substitution into a borane cage is common and
gives rise to an entire class of compounds (carboranes), silicon
substitution is rather rare. There are only few examples of
silaboranes which are directly related to carboranes by
substitution of silicon for carbon. The most convenient method for
the preparation of metallacarboranes is based on a reaction
between metallaboranes/boranes and alkynes. The new
millennium has witnessed the synthesis of the first stable examples
of homonuclear alkyne analogues of the heavier main group 14
elements, which in turn, makes it important to extend the scope of
this reaction. Main-group-element unsaturated organic
substrates, will be designed and their reactivity established with
group 5-9 metallaborane complexes.
Furthermore, a comprehensive synthetic and performance
evaluation study of the compounds, if confirmed by XRD, will be
carried out with the aim of gaining insight about the geometryfunction
correlation of these complexes. Apart from the
aforementioned reactivity studies, a detailed structural study of
the complexes will be carried out to understand the structureproperty
relationship.
Intimately linked to these experimental studies will be parallel
c o m p u t a t i o n a l w o r k . T h e o r e t i c a l s t u d i e s o n
metallaheteroboranes using quantum chemical calculations will
reveal critical information on their formation, structures and
stabilities. Wherever possible computed structures and physical
properties (e.g. NMR shifts) will be correlated with their
measurable experimental equivalents. Computations will serve
as both rationalising and guiding the experimental work, with the
ultimate overall objective of establishing a firm understanding of
the systems synthesised.
Accomplishments
i) Interpretation of the molecular structure and electrochemical
properties of the metallaborane complex Cp*Ru(B H )RuCp*
8 14
(Cp* = 5-C5Me5) has begun. This compound is unexpectedly
apparented to pentalene complexes such as
Cp*Fe(C H )FeCp* (C H = pentalene) which possesses the
8 6 8 6
same valence electron count
η
C5Me5Mo) 2 B5H 6( μ3-OEt) and ( η -C5Me5Mo) 2 B5H 5( μ3-OEt)(n-
OBu) where oxygen is contiguously bound to both cluster
metals and boron atoms is currently theoretically studied, in
order to rationalise their electron count, their bonding, the
number of hydrogen atoms, and their NMR properties
ii) The electronic structure of the oxamolybdaborane clusters (
5
5
-
Research papers published: Nil
Project 4405-1
CHEMISTRY AND APPLICATION OF METALLASILA- AND
METALLAGERMABORANES DERIVED FROM GROUP 14
UNSATURATED ORGANIC SUBSTRATES
Research Activities 2010-11
Pure & Applied Chemistry
Prof. Sundargopal Ghosh
Department of Chemistry
Indian Institute of Technology Madras
Chennai
Prof. Jean-François Halet
Sciences Chimiques de Rennes
UMR 6226 CNRS-Université de
Rennes 1
Rennes
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