Chapter 1: IntroductionStructure and Bonding Types of Ligand Coordination

Three generic classes of ligands: L: a neutral electron pair donor (i.e., CO, PR3) X: an anionic electron pair donor (i.e., X , H ) M-M: neutral 1 electron donor Distinguishing L-type ligands from X-type ligands: To distinguish between X and L type ligands, consider removing ligand from metal center with the ligand taking the electron pair in the M-L bond. If the ligand in it's free state is neutral, it is an L-type ligand. If it would be anionic, it is X-type.
CH3 X-type

CH3 L-type N N Pd PMe3 Cl PMe3 L-type

Cl

X-type

Ligands that can donate more than one pair of electrons can be classified using L and X designations:
CH3 O L2 4 e donor N R LX 4 e donor H3C H3C CH3 CH3 L2X 6 e donor

Types of ligand coordination: Terminal: Ligand is bound to only one metal center (L-M or X-M) Bridging (): Ligand is attached to two different metal centers (M-L-M or M-X-M). For L-type ligands, the lone pair is usually shared between the two metals (count 1 electron for each metal). For X ligands, the lone pair can also be shared. If the X ligand has additional lone pairs (i.e., halide, alkoxide), then the additional lone pairs can be used to coordinate to the second metal center. Hapticity (): Ligand attached to a metal center through more than one atom. Generally used to describe ligands with conjugated -systems

M !4

M !5

M !6

Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL

Chapter 1: Structure and Bonding: 2

Hapticity for ligands such as Cp can be variable depending on how it is coordinated. Usually Cp 5 3 1 is a -L2X ligand, but it can also coordinate as an -LX, or even an -X. The process of going 5 3 from to is often called ring slippage. Chelation: Ligand attached through more than one atom usually separated by one or more atoms. Chelating ligands are sometimes classified as being bidentate (2 points of attachment), tridentate (three points of attachment), or tetradentate (4 points of attachment).
Cl Me2 N Pt Cl N Me2 !2N-coordination bidentate ligand Cl S P Fe S S !P, !3S-coordination tetradentate ligand

Kappa convention (): The kappa convention is sometimes used to indicate the coordinating atoms of a polydentate ligand. If only some of the possible coordination sites are bonded to the metal, the coordinating atoms are indicated with a kappa. Some authors use kappa to indicate how many of the coordinating atoms are attached in a polydentate ligand.
!3-[N,N'-di(2-aminoethyl)ethane 1,2diamine]chloroplatinum ion or [N-(2-amino-!N-ethyl)-N'-(2aminoethyl)ethane 1,2-diamine!2N,N']chloroplatinum ion

NH Pt N NH H2 Cl NH2

The 18-Electron Rule Recall: First row elements have 4 valence orbitals (1 s + 3 p) so they can accommodate up to 8 valence electrons--the octet rule. Transition metals have 9 valence orbitals (1 s + 3 p + 5 d). Upon bonding to a ligand set, there will be a total of 9 low lying orbitals (see MO theory discussion below). Therefore, we can expect that the low lying MOs can accommodate up to 18 valence electrons--The 18-Electron Rule. Organometallic complexes with 18 electrons are predicted to be particularly stable because they will have a closed shell of electrons. Complexes with 18 electrons are often referred to as being coordinatively saturated. Counting electrons: There are two models for counting electrons. Both give the same answer, but offer different advantages and disadvantages. Example: CH4 Covalent model: Since C-H bonds are covalent, assume that the electrons are shared equally between carbon and hydrogen. To count the electrons, we dissect the molecule giving each atom 1 electron of the bonding pair.

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Chapter 1: Structure and Bonding: 3

H H H C H H H C H
Ionic model: Alternatively, we can treat the bonds as being ionic. This allows us to assign a formal oxidation state to the carbon atom. This can be useful to determine whether a particular transformation is an oxidation or a reduction. In this model, both electrons are given to the atom with the higher electronegativity. For a C-H bond, this is the carbon.

H: 4 X 1 e = 4 C: 4e Total = 8 electrons

H H H C H H H C H
Similarly for a transition metal complex, the electron count is the sum of the metal valence electrons + the ligand centered electrons. Covalent Model: # e = # metal electrons + # ligand electrons - complex charge Metal: The number of metal electrons equals it's row number (i.e., Ti = 4e, Cr = 6 e, Ni = 10 e) Ligands: In general L donates 2 electrons, X donates 1 electron. See the table below. Ionic Model: # e = # metal electrons (d ) + # ligand electrons Metal: You must first determine the formal oxidation state of the metal. The number of electrons is 0 8 the row number minus the charge on the metal (i.e., Ti(4+): 4 - 4 = 0 e, d ; Pd (2+): 10 - 2 = 8 e, d ). The formal oxidation state is simply the charge on the complex minus the charges of the ligands. Ligands: In general and L and X are both 2 e donors. See the table below. The covalent model is used by Crabtree in his book. It may be more realistic in most cases, since M-L bonds are usually covalent, but does not indicate the formal oxidation state. In my opinion, the ionic model is easier and gives a clearer picture of the actual chemistry, since the formal oxidation state is part of the calculation. All discussions in this class will use the ionic model, so I would encourage you to learn that one. You should also be aware of the covalent method, since you will encounter it from time to time. Examples: HMn(CO)5 Covalent Model H = 1 e 5 X CO = 10 e Mn = 7 e Total = 18 e
n

4-

H+: 4 X 0 e = 0 C(-4): 8 e Total = 8 electrons

H OC OC CO Mn CO CO

Ionic Model H = 2e 5 X CO = 10 e 6 Mn(I) d = 6 e Total = 18 e

-

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Chapter 1: Structure and Bonding: 4

[CpFe(CO)]

Covalent Model Cp = 2 X CO = Fe = Charge (-1) = Total =

Ionic Model Cp = 2 X CO = 8 Fe(0) d = Total =

-

Fe OC CO

[CpNi(-CO)]2 Covalent Model Cp = 2 X 1/2 CO = Ni-Ni = Ni = Total =

O C Cp Ni C O Ni Cp

Ionic Model Cp = 2 X 1/2 CO = Ni-Ni = 9 Ni(I) d = Total =

-

Ligand Name

Covalent Model
Electron Count

lonic Model
Charge +1 0 Electron Count 2 2

Nitrosyl (linear, NO ), terminal or bridging) Carbene (CYR, where Y = substituent with interaction with carbene, i.e., OR, NR2, Ph, X Y M R CO, CNR (bridging or terminal) PR3, AsR3, SbR3, NR3, imines, nitriles, ethers, sulfides, etc. Terminal dinitrogren (N2)
2

3 2

2 2 2 2

0 0 0 0

2 2 2 2

()-Alkene ()-Alkyne
2

2
M

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Chapter 1: Structure and Bonding: 5

()-Carbonyl
H H

2 4

0 0 0

2 4 4

()-Dihydrogen - -Alkyne
4 2

M M

-acyclic diene

6 -Arene Hydride (H ) Terminal or bridging Alkyl ( CR3)

O
1 1 6

1 1 1

-1 -1 -1

2 2 2

-Acyl M -Aryl, alkenyl, or alkynyl ER3 or EX3 (E = Si, Ge, Sn) Alkoxide ( OR), thiolate ( SR), amide ( NR2), or phosphide ( PR2) Superoxide M
-

1 1 1 1
-

-1 -1 -1 -1 -1 -1 -1 -1 -1

2 2 2 2 2 4 4 4 4

O
-

O
-

Halide (F , Cl , Br , I ) or pseudohalide ( CN, OTs, etc) Bridging alkoxide, thiolate, amide, or phosphide Bridging Halide (-X) M-X-M
O

1 3 3 3 3

-Acyl
2

-Alkenyl (terminal or bridging) M

M Terminal M Bridging
M

3 5

-1 -1

4 6

-Allyl

-Cyclopentadienyl (Cp )

M
2 -2 4

Carbene (CR2 where R = substituent with no Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL

Chapter 1: Structure and Bonding: 6

R M

interactions with the carbene carbon)

R C R M M

-2

-CYR or CR2 Imide (M=NR) Oxide (M=O)

2 2
M O O

-2 -2 -2 -3 -3

4 4 4 6 6

2 3 3

Peroxide (terminal or bridging) Alkylidine or carbyne, terminal

R C M M M

M C R

-Alkylidine Nitride
M N

-3

Application of the 18-electron rule: The 18-electron rule can be used as predictor for the number of ligands a particular metal will coordinate. V(CO)6 d
5

Cr(CO)6 d
6

(CO)5Mn-Mn(CO5 d
7

Fe(CO)5 d
8

(CO)3Co(-CO)2Co(CO)3 d
9

Ni(CO)4 d
10

17 e 18 e 18 e 18 e 18 e 18 e The 18 electron rule works best for low-valent metals with small ligands that are strong donors and/or acceptors (i.e., H and CO). These ligands give large , thus there is a strong preference for filling the d orbitals (requiring 18 electrons), and are small enough to allow the metal to be coordinatively saturated. For complexes that follow the 18 electron rule, it can be used to predict reactivity as we will see throughout the semester. Note, that just like the octet rule, the 18-electron rule is not an absolute requirement. There are many exceptions. Common exceptions to the 18 electron rule: d metals: The d metals (groups 8 - 11) have a tendency to form square-planar 16 electron complexes. This tendency is weakest for group 8 (Fe(0), Ru(0), and Os(0)) and is very strong for 8 groups 10 and 11 (Pd(II), Au(III)). Square planar, 16 electron complexes of of d metals results in completely filled orbitals except the high energy d x 2 y 2 (see MO discussion below).
8 8

PMe 3 Me Pd Me PMe 3
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CO Me3P Rh Cl CO Me3P

CH3 Au CH3 CH3

Chapter 1: Structure and Bonding: 7

0 0

d metals: The high-valent d complexes often have lower electron counts than 18.
3 X Np- = 6 carbene = 4 Ta(V) d0 = 0 Total = 10 e 2 X Cp- = 12 e 2 X CH3- = 4 e Zr(IV) d4 = 0 e Total = 16 e

Ta

Zr

CH3 CH3

Bulky Ligands: Sterically demanding ligands will often result in lower than expected electron counts.
t-Bu t-Bu t-Bu P Pd P t-Bu t-Bu t-Bu

> 18 electron complexes: Complexes with formally 19 or 20 electrons are known, but they are usually unstable, or adopt alternate configurations.

-e Co E = -.94 V vs SCE 18 e 19 e 20 e 18 e Co Ni Ni

Properties of Transition Metals Ionization potential: Row trends: General trend that IP increases (harder to oxidize) moving to right across transition series. Column trends: Trends across the series are not consistent. For middle and late transition metals generally third row elements best able to form higher oxidation states (+3) than second, which is greater than first row elements. High oxidation states are rare for first row elements, but nd rd more accessable for 2 or 3 row elements. Bond Stengths: Metal-ligand bond strengths tend to increase moving down a given column Formal Oxidation State and d electron configuration Oxidation states in organometallic complexes are merely formalisms that may bear little resemblance to the actual positive charge on the metal. "Formalisms are convenient fictions which contain a piece of the truth--and it is so sad that people spend a lot of time arguing about the deductions they draw, often ingeniously and artfully, from formalisms, without worrying about their underlying assumptions." (Roald Hoffman, JACS, 1984, 106, 2006) Consider the range of possible formal charges on metal centers: 2[Fe(CO)4] (Collman's reagent): Fe(-II), although the metal likely has little if any negative charge 2[ReH9] : Re(VII), although it is made by reduction of ReO4 (also Re(VII)) with sodium in ethanol

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Chapter 1: Structure and Bonding: 8

Therefore, formal oxidations and reductions do not necessarily result in a decrease or increase in electron density at the metal center. Conversely, reactions where the oxidation state does not change can greatly affect the electron density of the metal center.
Fe(CO)42Fe(-II), d10 18 e H+ HFe(CO)4Fe(0), d8 18 e H (Cy3P)2IrH5 Ir(V), 18 e d4 H+ Cy3P H H H Ir PCy3 H H 2 H2 = 4 e 2 H- = 4 e 2 PCy3 = 4 e Ir(III) d6 = 6 e Total = 18 e Oxidation by protonation

Reduction by protonation

For -coordinated ligands (i.e., alkenes, dienes, etc.) a number of different formal oxidation states can be determined. In the butadiene complex below, the ligand can either be considered an L2 ligand donating 4 electrons, an LX2 donating 6 electrons, or an X4 ligand donating 8 electrons. Therefore, the iron center can be Fe(0), Fe(II), or Fe(IV). In each case the complex has 18 electrons.

Fe OC CO CO
Fe(0), d8

Fe OC CO CO
Fe(II), d6

Fe OC CO CO
Fe(IV), d4

The d-electron count is a closely related formalism. The d-electron count is obtained by subtracting the charge on the metal from the row number. Although a formalism, the d-electron count can be used to predict the structure of organometallic complexes in some cases.

Coordination Number 2 3

Geometry
Linear T-Shaped

Preferred d

Example
Ph3P Au Cl

Pt-Bu3 Ph Pd Br

Trigonal

d ,d ,d

10

PPh3 Pd Ph3P PPh3

PPh3 Pd Ph3P PPh3 PPh3

Tetrahedral

d ,d ,d

10

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Chapter 1: Structure and Bonding: 9

Square Planar

PPh3 H3C Pd Cl PPh3

CO

Trigonal Bipyramidyl

d , d (distorted)

OC

Fe CO CO

CO CO

Octahedral

d ,d ,d ,d

OC OC

Mo CO

CO CO

Dodecahedral

Me3P H

PMe3 H Mo H H PMe3 Me3P

2-

Tricapped Trigonal Prism

H H H H H Re H H HH

To explain the bonding of ligands to metals, we have to consider the molecular orbitals involved metalligand bonding. Before the development of molecular orbital theory, the interaction of ligands with metals was described using crystal field theory. We'll discuss this briefly and then consider the true orbital interactions. Crystal Field Theory Assumption: Ligands act as points of negative charge surrounding the metal center For an isolated metal ion, the 5 d orbitals are degenerate. As an octahedral set of ligands approach, the d orbitals pointing along the x, y, and z axes ( d z 2 , d x 2 y 2 ) are destabilized. The other orbitals (dxy, dyz, and dxz) are less destabilized.

Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL

Chapter 1: Structure and Bonding: 10

eg

dz2

dx2-y2

t2g

dxy

dxz
eg

dyz

t2g ML6n+ Mn+ eg orbitals (d ) can form bonds with the ligands t2g orbitals (d ) can form bonds with the ligands

Crystal field splitting of other common geometries:

Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL

Chapter 1: Structure and Bonding: 11

Tetrahedral

Square Planar

dx2-y2

dxy

dyz

dxz

dz2

dxy

dx2

dx2-y2

dxz

dxz

dxy, dyz, dxz

dx2-y2

dz2 dxy dx2-y2 and dz2 Tetrahedral
High spin and Low spin complexes Co(III) has the electron configuration [Ar]3d 4s as a free atom. Upon coordination, the 4d orbitals are 6 0 stabilized relative to the 3s and the metal takes on a [Ar]3d 4s electronic configuration. This 6 configuration is usually shortened to d . A d electronic configuration would be expected to strongly favor an octahedral ligand arrangement, since this would result in the a completely filled set of the low-lying d (t2g) orbitals. This electronic configuration is called the low-spin form, since all electron spins are paired. If is small enough, though, a high-spin form with a t2g eg configuration is possible. In this configuration there are 4 unpaired electrons. Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL
4 2 6 4 2

dyz and dxz Square Planar

Chapter 1: Structure and Bonding: 12

eg

!
t2g Low-spin

eg

!
t2g High-spin

The size of the ligand field splitting () is dependent on the ligands as well as the metal center. nd rd 2 and 3 row transition metals tend to have higher Higher oxidation state metals have higher -acceptor and strong -donor ligands give high , while -donor ligands give low

I- < Br - < Cl- < F- < H2O < NH 3 < PPh 3 < CO, H < SnCl3-donor -acceptor/ strong !-donor Increasing "
Ligand Field Theory Crystal Field Theory is qualitative. To get a better understanding we can turn to a MO picture of bonding in coordination complexes. For an octahedral complex of pure donor ligands, the s, three p, and five d orbitals of the metal interact with the lone pair orbitals of the ligand. 6 of the metal orbitals (s, three p, and 2 d ) are of the appropriate symmetry to interact with the ligand orbital set. Therefore, a set of 6 bonding M-L MOs and 6 anti-bonding M-L * MOs are formed. The three d do not find a symmetry match and remain as non-bonding orbitals. As a result, an octahedral complex can accommodate 18 electrons in the bonding and non-bonding orbitals. We will see that this maximum is similar to the octet rule in the first row elements.

An octahedral d metal complex will have 18 valence electrons. The 6 ligands will each contribute 2 electrons (12 total) and the metal will contribute 6. These 18 electrons will fill all of the bonding orbitals (6 bonds) plus the three non-bonding dP orbitals (assuming a low spin complex). Note that in a high-spin complex the filled e2g orbitals are actually M-L antibonding orbitals.

Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL

Chapter 1: Structure and Bonding: 13

M-L "*

Deg

eg

!
t2g

Mn+

Deg

6 ligand lone pairs M-L "

ML6n+

Types of Ligands -donors: Typical M-L bonding arrangement. Lone pair orbital of ligand interacts with metal orbitals. -acceptors: Ligands such as CO have empty MOs of proper symmetry to overlap with the filled d orbitals of the metal center. CO is an example of a -acceptor ligand (often called a -acid). In the case of CO, the * MO of CO is the orbital that interacts with the metal d. In the MO description above, the CO * orbitals will interact with the Md orbitals. This interaction stabilizes the filled Md orbitals. As a result of this bonding interaction, the metal is donating electron density back to the ligands in a process called back bonding. acceptors form very strong M-L bonds due to this back bonding -acceptors increase the ligand splitting by stabilizing the t2g set of orbitals increasing - back bonding allows electron density to be donated back to the ligand. This allows low-valent metals with filled d orbitals to form complexes with ligands

Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL

Chapter 1: Structure and Bonding: 14

M-L " *

M-L !

Other -acceptor ligands: NO, N2, CN-R, PF3

! ! d

-donors: Ligands with lone pairs on the coordinating atom (i.e., OR, X, NR2) can act as -donor ligands. The atom can rehybridize to place the lone pairs in orbitals with symmetry that can overlap with the metal d orbitals. As a result, the number of electrons that can be donated by these ligands will depend on how electron deficient the metal is. For example, oxygen could donate 2, 4, or 6 electrons. This concept will be further developed in the next chapter of notes.
-

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Chapter 1: Structure and Bonding: 15

M-L ! d! p

M-L "

For a metal with filled d orbitals, -donation will result in a destabilization of these orbitals due to repulsion between the lone pair electrons and the d electrons. This results in a smaller and a weaker M-L bond.

d Ligand lone pairs

For d metals, such as W , -donation is a favorable interaction and leads to stronger M-L bonds.

6+

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Chapter 1: Structure and Bonding: 16

-complexes: Unsaturated molecules can donate electrons to form M-L bonds rather than non-bonding lone pairs. Ethylene is a classic example.
M-L ! *

d H Cl Cl Cl H H Zeise's Salt--1825 Organometallics, 2001, 20, 2-6

M-L "

H C M C H

Pt

The orbital of ethylene acts as a donor. The * orbital of ethylene is of the proper symmetry to act as a -acceptor (back bonding). Any compound with a bond can potentially form a complex with a metal center (alkynes, arenes, ketones, etc.) -complexes: Dihydrogen can bind to metal centers as an intact molecule. H2 has neither lone pairs nor electrons. The electron pair that interacts with the metal center is the -bonding electrons of the H-H bond. The orbital can act as a -acceptor allowing back bonding to occur.

M-L #

d
!"

H M H
M-L ! !

Other -complexes that have been identified include: C-H, Si-H, Sn-H, P-H, S-H, B-H, M-H Prepared by Dr. Kevin Shaughnessy, Spring 2011 The University of Alabama, Tuscaloosa, AL