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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
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
Intro 23
Ligands, Bonding Types, Charges, and Electron Donor Numbers
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
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
Intro 26
Isocyanide: CN-R M C N R 0 2
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
Intro 27
Aryl: C6H5 -1 2
1 terminal M
Alkenyl (vinyl): -1 4
CH=CH2 M
2 terminal
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
Intro 28
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
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)