This document provides an introduction to organometallic chemistry. It defines organometallic compounds as those containing direct metal-carbon bonds. Common examples like ferrocene are shown. Carbon monoxide is discussed as an important ligand that stabilizes low oxidation state metals. The 18-electron rule for predicting structures of metal carbonyl complexes is explained through examples like Cr(CO)6. Synthesis of metal carbonyls from carbon monoxide and various metal precursors is also covered.
This document provides an introduction to organometallic chemistry. It defines organometallic compounds as those containing direct metal-carbon bonds. Common examples like ferrocene are shown. Carbon monoxide is discussed as an important ligand that stabilizes low oxidation state metals. The 18-electron rule for predicting structures of metal carbonyl complexes is explained through examples like Cr(CO)6. Synthesis of metal carbonyls from carbon monoxide and various metal precursors is also covered.
This document provides an introduction to organometallic chemistry. It defines organometallic compounds as those containing direct metal-carbon bonds. Common examples like ferrocene are shown. Carbon monoxide is discussed as an important ligand that stabilizes low oxidation state metals. The 18-electron rule for predicting structures of metal carbonyl complexes is explained through examples like Cr(CO)6. Synthesis of metal carbonyls from carbon monoxide and various metal precursors is also covered.
This document provides an introduction to organometallic chemistry. It defines organometallic compounds as those containing direct metal-carbon bonds. Common examples like ferrocene are shown. Carbon monoxide is discussed as an important ligand that stabilizes low oxidation state metals. The 18-electron rule for predicting structures of metal carbonyl complexes is explained through examples like Cr(CO)6. Synthesis of metal carbonyls from carbon monoxide and various metal precursors is also covered.
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Organometallic
Chemistry CHEM 20312 Dr. Mark Whiteley 4.02g Mark.Whiteley@manchester.ac.uk Office Hour (weeks 9-12) Wednesday 9.00am 1
Recommended Texts M Bochmann, 'Organometallics 1', Oxford Chemistry Primers, No. 12. M Bochmann, 'Organometallics 2', Oxford Chemistry Primers, No. 13. C. Elschenbroich, 'Organometallics', 2nd or 3rd eds, VCH. Housecroft and Sharpe 4th Edition Chapters 24 and 25 2
What defines an Organometallic Complex?
[Fe(-C5H5)2]
Ferrocene
[RhI2(CO)2]-
[As2(CH3 )4]
They ALL have a DIRECT metal carbon bond
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Definition of Organometallic Compounds Organometallic chemistry: chemistry of molecules containing Metal-Carbon bonds. This course considers d-block (transition) metals but main group organometallics of Li, Mg (Grignard) Hg and Sn also very important synthetic reagents. M is often in low oxidation state (+2, +1, 0 or even negative), hence electron-rich. Stabilised by electron-acceptor ligands. 4
Importance of Organometallic Chemistry: (i) Catalysis Monsanto process: MeOH/CO/ Rh cat. MeCO2H (acetic acid) Hydroformylation: RCH=CH2 / CO/H2/ Rh cat. RCH2CH2CHO (aldehyde) Ziegler-Natta process: CH2=CH2 Ti cat. polyethylene All work because the organic molecules are coordinated and activated by the metal catalyst. Homogeneous systems have advantages of mild operating conditions and high product specificity. 5
(ii) Organic Synthesis:
1. Isolation of reactive organic
molecules as metal-coordinated species eg. carbene, cyclobutadiene. 2. Reactivity modification via transition metal coordination eg activation of alkenes and arenes to nucleophilic addition. 6
Metal Carbonyl Complexes M(CO)n
Carbon Monoxide (CO) acts as a good ligand to
d-block transition metals.
The CO ligand has zero formal charge and
donates an electron pair (2 electrons) to the metal centre. CO acts as a strong -acceptor ligand and therefore stabilises complexes with metals in a low oxidation state Metal carbonyl complexes are important as starting materials for a wide range of organometallic complexes via ligand substitution reactions 7
Synthesis of Metal Carbonyl
Complexes 1. Direct reaction of CO with the metal powder
Ni + CO
1 atmosphere CO, 25C
Ni(CO)4
100 atmosphere (bar) CO, 150C
Fe(CO)5 Fe + CO
2. Reduction of a metal halide in a CO atmosphere
VCl3
Diglyme, 300 bar
+ 3Na + CO
[V(CO)6]
Diglyme = Di(2-methoxyethyl) ether
Benzene WCl6 + 2Et3Al + CO W(CO)6 70 bar, 50C
Structures of first row d block (3d)
homoleptic metal carbonyls
Bridging 2-CO
Terminal CO 10
Trends in metal carbonyl
structures The 18-electron rule
Cr group 6 Cr(0) d6
Fe group 8 Ni group 10 Fe(0) d8 Ni(0) d10
6 CO = 12 e5 CO = 10 e4 CO = 8 e Total 18 e Total 18 e Total 18 e 11
The 18-electron rule
Metal valence d electrons + ligand electrons donated to metal sum to 18 (filled s, p and d orbitals on metal) Applies to complexes with good acceptor ligands (eg CO) Some exceptions especially 17- and 16- electron systems (see later). Can be used to predict structures of organometallics.
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Examples of electron counting:
1. Cr(CO)6 Group
Number of e-
Cr0
CO x 6
12
Total
18
13
2. Mn2(CO)10 (Metal-metal bonding) (Mn d7 has an uneven (odd) number of valence d electrons) Mn0
CO x 5
10
Mn Mn
Total
18
Formation of a Mn-Mn metal-metal bond adds an extra electron to the count at each metal
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3. Fe2(CO)9 (Bridging carbonyl
ligands) Fe0
Terminal CO
Bridging CO
COterminal x 3
8 6
CObridging x 3
MM
Total
18
2-bridging CO ligands provide 1 electron to each metal centre.
Bridging CO usually observed for smaller metal centres: (i) First row (3d) metals (ii) metals on right hand side of d block eg 15 Co not Mn
4. Na[Mn(CO)5] (Charged species)
-
O C OC O
Mn
C C O
CO
Mn
CO x 5
10
negative charge
Total
18
In Na[Mn(CO)5] the anion [Mn(CO)5] is present.
Count by adding one extra electron for the negative charge. 16
5. [V(CO)6] (An anomalous case)
v
O C OC O
C C O
CO x 6 Total
5 12 17
V(CO)6 is a 17-electron radical (has an unpaired
electron and does not obey the 18-electron rule). Readily reduced to 18-electron [V(CO)6] V-V bonded bimetallic not formed 17
6. [Ru3(CO)12] (A metal cluster)
O
O C Ru C O
C Ru
OC OC
O C CO O C
C O
CO
Ru C O
Ru
CO x 4 Ru-Ru x 2
8 2
Total O
18
Metal cluster: more than 2 metals in complex
Ru group 8 (like Fe) d8 All CO terminal (larger 4d metal reduces possibility of bridging) 18
7. Mo(CO)n (Use of the 18-electron rule
to predict molecular formula) Mo is a group 6 metal (like Cr) Mo(0) d6 Mo(CO)n obeys 18-electron rule. Each CO provides 2 electrons to Mo 6 (Mo) + n x 2 = 18 n = 6. Formula is Mo(CO)6
