The document discusses boranes and carboranes. It defines boranes as binary compounds of boron and hydrogen. Carboranes are mixed hydrides of boron and carbon that have similar structures to boranes. The document covers the structures, bonding, and applications of various types of boranes like closo, nido and arachno boranes. It also discusses Wade's rule for predicting borane and carborane structures.
The document discusses boranes and carboranes. It defines boranes as binary compounds of boron and hydrogen. Carboranes are mixed hydrides of boron and carbon that have similar structures to boranes. The document covers the structures, bonding, and applications of various types of boranes like closo, nido and arachno boranes. It also discusses Wade's rule for predicting borane and carborane structures.
The document discusses boranes and carboranes. It defines boranes as binary compounds of boron and hydrogen. Carboranes are mixed hydrides of boron and carbon that have similar structures to boranes. The document covers the structures, bonding, and applications of various types of boranes like closo, nido and arachno boranes. It also discusses Wade's rule for predicting borane and carborane structures.
The document discusses boranes and carboranes. It defines boranes as binary compounds of boron and hydrogen. Carboranes are mixed hydrides of boron and carbon that have similar structures to boranes. The document covers the structures, bonding, and applications of various types of boranes like closo, nido and arachno boranes. It also discusses Wade's rule for predicting borane and carborane structures.
Department Of P.G. Studies and Research in Chemistry
Jnanasahyadri, Shankaraghatta.
SEMINAR ON BORANES AND CARBORANES
PRESENTED BY Arun Chikkodi. I M.Sc., Department of Chemistry Jnanasahyadri, Shankaraghatta. CONTENTS Introduction Boranes Diborane Types of boranes Bonding and structure in boranes Carboranes Types of carboranes Wade’s rule Applications INTRODUCTION The binary compounds of boron and hydrogen are called boranes. Boranes were first prepared between 1912 and 1936, by Alfredstock, who developed vacuum line techniques to handle these relative materials. Boranes are the name to class of synthetic hydrates of boron. The molecules of these compounds are electron deficient and so reactive with respect to electron donors. Many boranes synthesised from thermolysis of B2H6 .All boranes are diamagnetic and colourless. BORANES The parent member BH3 is called borane, is found only in the gaseous state, and dimerizes to form diborane, B2H6.
General formula of boranes is BxHy
The most important boranes are diborane B2H6, pentaborane B5H9, and decaborane B10H14. Boranes are all colourless and diamagnetic, And some are pyrophoric.
Boranes are highly reactive.
Common reactions with boranes are: electrophilic substitution, nucleophilic
substitution by Lewis bases, deprotonation by strong bases, cluster building reactions with borohydrides, and reaction of a nido-borane with an alkyne to give a carborane cluster. DIBORANE • Diborane is simplest and most studied of boranes. It is an electron deficient molecule . • It has less number of valence electrons than the H number required to form all the electron pair bond in its H B B H structure.2 hydrogen bridges are present. H H • The model determined by MOT indicates that the bond H between boron & terminal hydrogen atoms are conventional 2c-2e electron bonds. • Having used 2 electrons in bonding to terminal hydrogen atoms. Each boron has one valence e- remain for additional bonding. The bridging hydrogen provides an electron each. Thus B2H2 ring is held together by 4 electrons. BONDING AND STRUCTURE IN DIBORANE The diborane molecule has 2 type of bonds. • 1. four terminal (2c-2e) B-H bonds. • 2. two bridged (3c-2e) B-H-B bonds.
• 1. four terminal (2c-2e) B-H bonds.
Each of these bonds are formed by sharing of 2 electrons between boron and terminal hydrogen atoms. It’s a normal 𝜎 covalent bond. • 2. two bridged (3c-2e) B-H-B bonds. Each of these bond is formed by sharing of 2 electrons between 2 B and 1 H atoms . • It is also called as banana bond TYPES OF BORANES CLOSO BORANES
Closed, triangulated polyhedra structure.
All corners of triangulated polyhedra are
occupied.
General formula: BnHn+2,
Example: [B6H6]2- NIDO BORANES
nido boranes are formed when
one corners of the polyhedra is removed. nest like, non-closed structure General formula: BnHn+4, Example: B5H9, B2H6 ARACHNO BORANES
These boranes are formed when two
corners of the polyhedra is removed .
Web like ,non-closed polyhedra
structure
General formula: BnHn+6,
Example: [B4H10] HYPO BORANES Hypo- net like These have most open clusters in which Boron atoms occupy n corners of(n+3) polyhedron General formula: BnHn+8 these boranes are having complex structures. Example : B8H16 and B10H18
CONJUCTO BORANES These boranes formed by linking of 2 or more of any other type of boranes. These structures are very complex General formula : BnHm Example: (B5H9)2 , (B4H10)2 BONDING IN BORANES 2c-2e bond B . .H 3c-2e bond B------H.------.B B.------.H------B
In boranes 4 types of bonds are present
H 1. 3c-2e B-H-B B B Bent 2. 3c-2e B-B-B B B B Open B B B Closed
3. 2c-2e B-B Normal
4. 2c-2e B-H Normal STYX CODES The over all boranes bonding can be represented by 4 digital numbers S = number of B-H-B bonds (1st digit ) T = number of B-B-B bonds (2nd digit) Y = number of B-B bond (3rd digit) X = number of B-H2 groups (4th digit)
Ex: B2H6 (Diborane)
S = number of B-H-B bonds = 2 H T = number of B-B-B bonds = 0 H B B H Y = number of B-B bond = 0 H H H X = number of B-H2 groups = 2 Hence for diborane styx code is 2002. Example – B4H10 styx code is 4012 CARBORANES • Carboranes are mixed hydrides of boron and carbon in which carbon and boron atoms occupy the vertices of triangulated polyhedron.
• Carboranes are most important heteroboranes.
• Carboranes are member of a class of organometallic compounds containing
carbon (C), boron (B), and hydrogen (H).
• General formula of carboranes is C2BnHn+m, where n is an integer
• carboranes with n ranging from 3 to 10 have been characterized.
• Boranes and carboranes have same number of electrons in their bonding
framework , will have similar structure. TYPES OF CARBORANES CLOSO CARBORANES Closed, triangulated polyhedra structure.
General formula: C2BnHn+2,
Total number of electron in bonding framework
is (2n+2)e-. i.e. (n+1) e pairs.
Example-1,6-C2B8H10 NIDO CARBORANES
One corner of triangulated polyhedra is
removed
General formula: C2BnHn+4,
Total number of electron in bonding framework
is (2n+4)e-. i.e. (n+2) e- pairs.
Example- C2B4H8, [1,7-C2B9H12]-
ARACHNO CARBORANES
• Two corners of triangulated polyhedra is removed.
• General formula: C2BnHn+6,
• Total number of electron in bonding framework is
(2n+6)e-. i.e. (n+4) e- pairs.
• Example- 1,3-C2B7H13 WADE’S RULE In chemistry polyhedral skeletal electron pair theory provides electron containing rules useful for predicting structures of boranes and carboranes. It is formulated by Wade and hence it is called as Wade’s rule. In Wade’s rule i. Each BH unit donates 2e- to skeletal structures. ii. Each CH unit donates 3e- . iii. -ve charge on borane gives an electron. iv. Additional hydrogen atom gives one electrons each.
Types Formula Skeletal Electron Example
Pairs Closo BnHn n+1 [B5H5]2- Nido BnHn+4 n+2 B2H6 Arachno BnHn+6 n+3 B4H10 Hypho BnHn+8 n+4 None APPLICATIONS OF BORANES AND CARBORANES • Boranes are used as rocket fuels in supersonic aeroplanes.
• Used as catalyst in polymerisation reaction
• Used as reducing agent in organic reactions
• Boranes can be used as vulcanising agent for natural and synthetic
rubber.
• Used in borane coating
CONCLUSION • Boranes are colourless and gaseous at room temperatures.
• Boranes are highly reactive and reacts violently with water.
• In boranes 3c-2e bonds are present; It is unique type of bond present in
boranes only.
• Carboranes are mixed hydrides of boron and carbon. And have same structure like boranes.
• Carboranes derived from pyrolysis of boranes
REFERENCES • Inorganic chemistry, Peter Atkins, Tina Overton, Jonathon Rourke, Mark Weller, Fraser Armstrong, 5th Edition, Oxford University Press, UK, 2013. • Inorganic chemistry, Gary L. Miessler, Donald A Tarr, 3rd Edition, Pearson Education, NewDehli ,India, 2004. • Inorganic chemistry-Principles of Structures and Reactivity, James E. Huheey, Ellen A. Keiter, Richard L. Keiter, 4th Edition, Pearson, India Edition, NewDehli ,India, 2004. • Advance Inorganic Chemistry, F. Albert Cotton, Geoffrey, Wilkinson, Carlos A. Murillo, Manfred Bochmann, 6th Edition, Wiley Student Edition, John Wiley and Sons, INC, NewYork, 2004.
