Sei sulla pagina 1di 46

Chapter 15 Parallels Between Main Group and Organometallic Chemistry

15-1 Main group parallels with binary carbonyl complexes

15-2 The isolobal analogy

15-3 Metal-metal bonds

15-4 Cluster compounds

15-1 Main group parallels with binary carbonyl complexes

Consider several parallels between main group and organometallic compounds.

several parallels between main group and organometallic compounds . 7 electrons 17 electrons Electronically equivalent

7 electrons

17 electrons

Electronically equivalent

15-1 Main group parallels with binary carbonyl complexes

15-1 Main group parallels with binary carbonyl complexes
15-1 Main group parallels with binary carbonyl complexes
15-1 Main group parallels with binary carbonyl complexes

15-1 Main group parallels with binary carbonyl complexes

15-1 Main group parallels with binary carbonyl complexes
15-1 Main group parallels with binary carbonyl complexes

15-1 Main group parallels with binary carbonyl complexes

15-1 Main group parallels with binary carbonyl complexes Tetrahedral tetramers
15-1 Main group parallels with binary carbonyl complexes Tetrahedral tetramers

Tetrahedral tetramers

15-2 The isolobal analogy

Ronal Hoffmann in his 1981 Nobel lecture;

Hoffmann defined molecular fragments to be isolobal

if the number, symmetry properties, approximate energy and shape of the frontier orbitals and the number of electrons in them are similar-not identical, but similar.

15-2 The isolobal analogy

Orbitals of octahedral and tetrahedral fragments
Orbitals of octahedral and tetrahedral fragments

15-2 The isolobal analogy

15-2 The isolobal analogy

15-2 The isolobal analogy

Cyclic trimers
Cyclic trimers
15-2 The isolobal analogy Cyclic trimers
15-2 The isolobal analogy Cyclic trimers

15-2 The isolobal analogy

15-2 The isolobal analogy The isolobal species Ir(CO) 3 , Co(CO) 3 , CR, and P

The isolobal species Ir(CO) 3 , Co(CO) 3 , CR, and P

isolobal species Ir(CO) 3 , Co(CO) 3 , CR, and P Structures resulting from combinations of

Structures resulting from combinations of Co(CO) 3 and CR

15-2-1 Extensions of the analogy

1. The isolobal definition may be extended to isoelectronic fragments having the same coordination number.

Mn(CO) 5

fragments having the same coordination number. Mn(CO) 5 CH 3 , Re(CO) 5 [Fe(CO) 5 ]+

CH 3 ,

Re(CO) 5 [Fe(CO) 5 ]+ [Cr(CO) 5 ]-

5 CH 3 , Re(CO) 5 [Fe(CO) 5 ]+ [Cr(CO) 5 ]- CH 3 2. Gain

CH 3

2. Gain or loss of electrons from two isolobal fragments yields isolobal fragments.

Mn(CO) 5

two isolobal fragments yields isolobal fragments. Mn(CO) 5 CH 3 , Cr(CO) 5 Mo(CO) 5 W(CO)

CH 3 ,

Cr(CO) 5

Mo(CO) 5

W(CO) 5

Fe(CO) 5

Ru(CO)

Os(CO)

5

5

CH 3 3

+

CH 3 3

-

15-2-1 Extensions of the analogy

3. Other 2-electron donors are treated similarly to CO

Mn(CO) 5

2-electron donors are treated similarly to CO Mn(CO) 5 Mn(PR 3 ) 5 [MnCl 5 ]

Mn(PR 3 ) 5

are treated similarly to CO Mn(CO) 5 Mn(PR 3 ) 5 [MnCl 5 ] 5 -

[MnCl 5 ] 5-

to CO Mn(CO) 5 Mn(PR 3 ) 5 [MnCl 5 ] 5 - Mn(NCR) 5 CH

Mn(NCR) 5

CO Mn(CO) 5 Mn(PR 3 ) 5 [MnCl 5 ] 5 - Mn(NCR) 5 CH 3

CH 3

4. Ligands η 5 -C 5 H 5 and η 6 -C 6 H 6 are considered to occupy three coordination sites and to be 6-electron donors

(η

(η

6

5

-C

-C

6 H 6 )Mn(CO) 2

5 H 5 )Fe(CO) 2

Mn(CO) 5 5

( η ( η 6 5 -C -C 6 H 6 )Mn(CO) 2 5 H 5

CH 3 ,

[Fe(CO) 5 ]+ 5 ]+

( η ( η 6 5 -C -C 6 H 6 )Mn(CO) 2 5 H 5

CH 3 ,

15-2-1 Extensions of the analogy

5. Octahedral fragments of formula ML n (where M has a d x configuration) are isolobal with square-planar fragments of formula ML n-2 (where M has a d x+2 configuration and L is a 2- electron donor).

Octahedral Fragments

Square-planar Fragments

ML n

ML n-2

Cr(CO) 5

d 6

Fe(CO) 4

n t s Square-planar Fragments M L n ML n-2 Cr(CO) 5 d 6 Fe(CO) 4

[PtCl 3 ]-

d 8

Pt(PR 3 ) 2

d

8

d

n t s Square-planar Fragments M L n ML n-2 Cr(CO) 5 d 6 Fe(CO) 4

10

15-2-1 Extensions of the analogy

5. Octahedral fragments of formula ML n (where M has a d x configuration) are isolobal with square-planar fragments of formula ML n-2 (where M has a d x+2 configuration and L is a 2- electron donor).

Comparison of square-planar fragments with octahedral fragments
Comparison of square-planar fragments with octahedral fragments

15-2-1 Extensions of the analogy

6 5 432 5 4 3 6 5 4 3 n-1 n-2 n-3
6
5
432
5
4
3
6
5
4
3
n-1
n-2
n-3

15-2-2 Examples of applications of the analogy

The 5-electron fragment CH is isolobal with P and other Group 15 atoms. A potential application of this relationship is to seek phosphorous- containing analogues to organometallic complexes containing cyclic ligands such as C 5 H 5 and C 6 H 6

containing analogues to organometallic complexes containing cyclic ligands such as C 5 H 5 and C

15-3 Metal-Metal Bonds

15-3 Metal-Metal Bonds Single, double, triple, and quadruple bonds We need to consider how metal atoms

Single, double, triple, and quadruple bonds

We need to consider how metal atoms can bond to each other

15-3-1 Multiple Metal-Metal Bonds

Main group –highest possible bond order –--- 3 How about transition metal?

group –highest possible bond order –--- 3 How about transition metal? Bonding interactions between metal d

Bonding interactions between metal d orbitals

15-3-1 Multiple Metal-Metal Bonds

Main group –highest possible bond order –--- 3 How about transition metal?

Bonds Main group –highest possible bond order –--- 3 How about transition metal? Relative energies of

Relative energies of orbitals

15-3-1 Multiple Metal-Metal Bonds

Main group –highest possible bond order –--- 3 How about transition metal?

possible bond order –--- 3 How about transition metal? Re(III) – 4 d electrons Occupied by

Re(III) – 4 d electrons

Occupied by ligand electrons

possible bond order –--- 3 How about transition metal? Re(III) – 4 d electrons Occupied by

15-3-1 Multiple Metal-Metal Bonds

eclipsed staggered Structures ?
eclipsed
staggered
Structures ?

Relative energies of orbitals

15-3-1 Multiple Metal-Metal Bonds

15-3-1 Multiple Metal-Metal Bonds Bond order and electron count
15-3-1 Multiple Metal-Metal Bonds Bond order and electron count

Bond order and electron count

15-3-1 Multiple Metal-Metal Bonds

15-3-1 Multiple Metal-Metal Bonds The effect of population of δ and δ * orbitals on bond

The effect of population of δ and δ* orbitals on bond distances can sometimes be surprisingly small.

15-3-1 Multiple Metal-Metal Bonds

Quintuple bonds

Chromium(I) complexes with extremely short metal-metal bonds

complexes with ex tremely short metal-metal bonds Formal shortness ration = 0.774 - Trans-bent geometry and

Formal shortness ration =

0.774

- Trans-bent geometry and apparent interactions

Influence of bridging ligands Nonlinearity More complex interactions

Science, 2005

JACS, 2007

Angew. Chem. Int. Ed., 2008

15-4 Cluster compounds

Some of boron compounds exhibit similarities in their bonding and structures to transition metal clusters.

15-4-1 Boranes

Each boron has four valence orbitals

---- total 24 boron orbitals

s and 3p

four valence orbitals ---- total 24 boron orbitals s and 3p 13 bonding orbitals (= 2n
four valence orbitals ---- total 24 boron orbitals s and 3p 13 bonding orbitals (= 2n

13 bonding orbitals (= 2n + 1)

7

bonding orbitals (= n + 1)

13 bonding orbitals (= 2n + 1) 7 bonding orbitals (= n + 1) 6 bonding

6

bonding orbitals (= n) – boron-hydrogen bonding

n + 1) 6 bonding orbitals (= n) – boron-hydrogen bonding 11 nonbonding or antibonding orbitals

11

nonbonding or antibonding orbitals

6 of the hybrids

7 among remaining 6 of the hybrids and 12 of the unhybrides

15-4-1 Boranes

15-4-1 Boranes

15-4-1 Boranes

Closo, nido, and arachno borane structure

Structures of closo, nido, and arachno boranes having 6 to 12 borons

15-4-1 Boranes

15-4-1 Boranes

15-4-2 Heteroboranes

Isoelectronic species such as the carboranes (carbaboranes) CH + unit is isoelectronic with BH.

15-4-2 Heteroboranes Isoelectronic species such as the carboranes (carbaboranes) CH + unit is isoelectronic with BH

15-4-2 Heteroboranes

Formally each C should be converted to BH

C 2 B 8 H 10

each C should be converted to BH C 2 B 8 H 10 B 10 H

B 10 H 12

B 10 H 12 - 2H +

8 H 10 B 10 H 12 B 10 H 12 - 2 H + =

=

Therefore closo

B 10 H 10 2-

Many derivatives of boranes containing other main group atoms

12 - 2 H + = Therefore closo B 10 H 10 2 - Many derivatives

15-4-3 Metallaboranes and metallacarboranes

C should be converted to BH

Fe(CO) 3 unit is isolobal with BH.

Organometallic derivatives of B 5 H 9
Organometallic derivatives of B 5 H 9
3 unit is isolobal with BH. Organometallic derivatives of B 5 H 9 Orbitals of isolobal
3 unit is isolobal with BH. Organometallic derivatives of B 5 H 9 Orbitals of isolobal

Orbitals of isolobal fragments BH and Fe(CO) 3

15-4-3 Metallaboranes and metallacarboranes

15-4-3 Metallaboranes and metallacarboranes

Comparison of C 2 B 9 H 11 2- with C 5 H 5 -
Comparison of C 2 B 9 H 11 2- with C 5 H 5 - .
As ligand
Carborane analogs of ferrocene.
and metallacarboranes Comparison of C 2 B 9 H 11 2- with C 5 H 5

15-4-3 Metallaboranes and metallacarboranes

15-4-3 Metallaboranes and metallacarboranes

15-4-4 Carbonly clusters

The approach used to describe bonding in boranes may also be applicable to bonding in carbonly clusters and other clusters.

Total # of valence electrons in cluster

=

# of electrons involved in framework bonding
# of electrons involved in
framework bonding

+

# of electrons involved in metal-ligand bonding

Related to the classification of the structure as closo, nido……

to the classification of the structure as closo, nido…… Four valence orbitals Closo-B 6 H 6

Four valence orbitals

Closo-B 6 H 6 2-

26 valence electrons = 14 + 12

Closo-B 6 H 6 2 - 26 valence electrons = 14 + 12 Nine valence orbitals

Nine valence orbitals

2 - 26 valence electrons = 14 + 12 Nine valence orbitals Five extra orbitals →

Five extra orbitals 10 more electrons per framework atom

86 valence electrons = 14 + 72

15-4-4 Carbonly clusters

15-4-4 Carbonly clusters n designates the number of framework atoms

n designates the number of framework atoms

15-4-4 Carbonly clusters

15-4-4 Carbonly clusters

15-4-4 Carbonly clusters

15-4-4 Carbonly clusters Seven metal-metal framework bonding pairs are the most common Metal cores for clusters
15-4-4 Carbonly clusters Seven metal-metal framework bonding pairs are the most common Metal cores for clusters

Seven metal-metal framework bonding pairs are the most common

Metal cores for clusters containing seven skeletal bond pairs.

metal-metal framework bonding pairs are the most common Metal cores for clusters containing seven skeletal bond

15-4-4 Carbonly clusters

The predictions of structures of transition metal-carbonly complexes, using Wade’s rules are often, but not always, accurate.

Co 4 (CO) 12

60 valence electrons nido
60 valence
electrons
nido

A trigonal bipyramid (the parent structure) with one position vacant

However, tetrahedral metal cores

15-4-4 Carbonly clusters

15-4-4 Carbonly clusters Ionic clusters of main group elements ( Zintl ions ).

Ionic clusters of main group elements (Zintl ions).

15-4-4 Carbonly clusters

An extension of Wade’s rules has been described for electron counting

mno rule – states that for a closed cluster structure to be stable, there must be m + n + o skeletal electron pairs, where

m = # of condensed (linked) polyhedra

n = total # of vertices

o = # of single-atom bridges between two polyhedra

A fourth term

p = # of missing vertices (e.g. p =1 for nido, p = 2 for arachno)

15-4-4 Carbonly clusters

m = # of condensed (linked) polyhedra

n = total # of vertices

o = # of single-atom bridges between two polyhedra

p = # of missing vertices (e.g. p =1 for nido, p = 2 for arachno)

B 12 H 12 2-

m = 1

n = 12

o = 0

p = 0

13 pairs

B 12 H 12 2 - m = 1 n = 12 o = 0 p

m = 2

n = 23

o = 1

p = 0

26 pairs

15-4-5 Carbide clusters

Carbon exhibits unusual coordination numbers and geometries not found in classic organic structures

and geometries not found in classic organic structures Carbide clusters Encapsulated carbon contributes its 4

Carbide clusters

not found in classic organic structures Carbide clusters Encapsulated carbon contributes its 4 valence electrons. 86

Encapsulated carbon contributes its 4 valence electrons.

86 electrons

15-4-5 Carbide clusters

The octahedral Ru 6 core has framework bonding orbitals of the same symmetry as in B 6 H 6 2- .

of the same symmetry as in B 6 H 6 2 - . The formation of

The formation of four C-Ru bonding orbitals

6 2 - . The formation of four C-Ru bonding orbitals Bonding interactions between central carbon

Bonding interactions between central carbon and octahedral Ru 6 .

. The formation of four C-Ru bonding orbitals Bonding interactions between central carbon an d octahedral

15-4-5 Carbide clusters

Examples of large clusters.
Examples of large clusters.

Encapsulated iron

Homework

Exercise 15-1~15-9

Problem 1, 2, 5, 6, 11, 21, 23, 25.