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Intro 15

Common Coordination Geometries

6-Coordinate: Octahedral (90 & 180 angles)


L L
L L L
M L M L M
L L L L
L
L L L
5-Coordinate: Trigonal Bypyramidal or Square Pyramidial
(90 & 120) (~100 & 90)
L axial L apical

L L L
L M equitorial M
L L L basal
L
4-Coordinate: Square Planar or Tetrahedral
(90 & 180) (109)

L L

L M L M
L
L
L L
Square planar geometry is generally limited to Rh, Ir, Ni, Pd,
Pt, and Au in the d 8 electronic state when coordinated to 2e-
donor ligands.
Intro 20

Octahedral Orbital Diagram


z L
L
x L M L
y L
L
p z px py

px py pz
s
*
dx2 -y 2 LUMO
s (lowest unoccupied
dz 2 molecular orbital)

HOMO
(highest occupied
molecular orbital)
Metal d d
Orbitals

Ligand
Orbitals

M-L bonding
Orbitals
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Ligands, Bonding Types, Charges, and Electron Donor Numbers

Ligand Name Bonding Type Formal Electrons


Charge Donated

Molecular Hydrogen: H2 H 0 2
M
H
Hydride: H M-H -1 2
Hydride: H H -1 2
M M
Halide: X M-X -1 2

Halide: X X -1 4
bridging (2 to
M M each M)
Halide: X X -1 6
3 bridging (2 to
M M each M)
M
Alkoxide, thiolate: OR, SR M- OR -1 2 or 4

Alkoxide, thiolate: OR, SR R -1 4


bridging (2 to
O
each M)
M M
Alkoxide, thiolate: OR, SR R -1 6
3 bridging O (2 to
each M)
M M
M
Peroxide: O22 O -2 4
2 M
O
Peroxide: O22 O O M -2 4
2 bridging
O
M O (2 to
M M
each M)
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Oxide, sulfide: O2, S2 M O -2 4


6
M O
Oxide, sulfide: O2, S2 O -2 4
bridging (2 to
M M each M)
Oxide, sulfide: O2, S2 O -2 6
3 bridging (2 to
M M each M)
M
Amine, phosphine, arsine: M-NR3 0 2
NR3, PR3, AsR3 M-PR3
Amide, phosphide:
M N M P -1 2
NR2, PR2 R R
R R
R 4
M N R
Amide, phosphide: RR -1 4
NR2, PR2 bridging: (2 to
P
each M)
M M
Imido: NR2 R -2 4 (bent)
M N
6 (linear)
M N R
Imido: NR2 R R -2 4 or 6
bridging (2 or 3 to
N N
each M)
M M M M
Imido: NR2 R -2 6
3 bridging N (2 to
each M)
M M
M
Nitride, phosphide: MN: -3 6
N3, P3
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Nitride, phosphide: N N -3 4 or 6
N3, P3, bridging (2 or 3 to
M M M M each M)
Nitride, phosphide: N -3 6
N3, P3, 3 bridging
M M
M
Nitrosyl: NO+ M N O +1 2
linear form

Nitrosyl: NO M N -1 2
bent form
O
Nitrosyl: NO+ O +1 1 to each
bridging metal
N
M M
Nitrosyl: NO+ O +1 1 to each
3 bridging metal
N
M M
M
Carbonyl: CO M C O 0 2

Carbonyl: CO O 0 2 to each
,2 mode C metal
M M
Carbonyl: CO O 0 1 to each
bridging metal
C
M M
Carbonyl: CO O 0 1 to each
3 bridging metal
C
M M
M
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Isocyanide: CN-R M C N R 0 2

Isocyanide: CN-R R 0 1 to each


bridging N metal
C
M M
Alkene: R2C=CR2 R R 0 2
2 bonding mode R C C R

M
Alkyne: RCCR R C C R 0 2 or 4
2 bonding mode

M
Alkyne: RCCR R R 0 2 to each
bridging C C
metal

M M
Dienes: R2C=CH-CH=CR2 0 4
4 bonding mode
M
Dienes: R2C=CH-CH=CR2 0 2 to each
bridging metal
M M
Benzene: C6H6 0 6
6 bonding mode
M
Ketones, aldehydes: R 0 2
2 bonding mode R C O

M
Alkyl: CH3, CH2R M CR 3 -1 2
1 bonding mode
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Alkyl: CH3, CH2R R R R -1 2


C (1 to
each M)
M M assuming no
agostic M-H
interactions

Aryl: C6H5 -1 2
1 terminal M

Alkenyl (vinyl), alkynyl: M R -1 2


CH=CH2, CCH
1 terminal M

Alkenyl (vinyl): -1 4
CH=CH2 M
2 terminal

Alkenyl (vinyl), alkynyl: M -1 4


CH=CH2, CCH (2 to
,2 terminal M R each M)
M M

Cyclopropenyl: C3H3 -1 4
3 terminal
M
Allyl: C3H5 -1 4
3 terminal
M

Allyl: C3H5 M -1 2
1 terminal

Pentadienyl: C5H7 -1 6
5 terminal

M
Pentadienyl: C5H7 -1 4
3 terminal

M
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Pentadienyl: C5H7 M -1 2
1 terminal

Cyclopentadienyl: C5H5 -1 6
5

M
M

Cyclopentadienyl: C5H5 -1 4
3

M
Carbene: =CYR R 0 2
where Y is a substituent M C
capable of interaction with
the carbene carbon atom Y

Alkylidene: =CR22 R -2 4
where no substituents capable M C
of bonding to the carbene
carbon atom are present R

Carbene: =CYR or =CR22 Y R -2 2 to each


bridging metal
C
M M
Carbyne or Alkyidyne: M C R -3 6
CR3

Carbyne or Alkyidyne: R -3 2 to each


CR33 bridging metal
C
M M
M
Intro 29

How do I Figure Out Ligand Charges & Donor #s ??


(without memorizing that !#&!@%$* entire list)

First, you should learn the charges and donor # for the common
ligands (this will significantly speed up your counting):
Cationic 2e- donor: NO (nitrosyl)
Neutral 2e- donors: PR3 (phosphines), CO (carbonyl), R2C=CR2
(alkenes), RCCR (alkynes, can also donate
4 e-), NCR (nitriles)
Anionic 2e- donors: Cl (chloride), Br (bromide), I (iodide), CH3
(methyl), CR3 (alkyl), Ph (phenyl), H
(hydride)
The following can also donate 4 e- if needed, but
initially count them as 2e- donors (unless they
are acting as bridging ligands): OR (alkoxide),
SR (thiolate), NR2 (inorganic amide), PR2
(phosphide)
Anionic 4e- donors: C3H5 (allyl), O2 (oxide), S2 (sulfide), NR2
(imido), CR22 (alkylidene)
and from the previous list: OR (alkoxide), SR
(thiolate), NR2 (inorganic amide), PR2
Anionic 6e- donors: Cp (cyclopentadienyl), N3 (nitride)

Please note that we are using the Ionic Method of electron-counting.


95% of inorganic/organometallic chemists use the ionic method.
The ionic method assigns formal charges to the metal and ligands in
order to keep the ligands with an even # of electrons and (usually) a
filled valence shell. There is also the neutral method that considers
everything to be neutral. Synthetically, the ionic method makes
more sense and the one that we will use in this course.