Chapter 15 Main Group/Organometallic Parallels (pp. 590-607)I. Main Group Parallels with Binary Carbonyl Complexes

A. Previously discussed organic/main group parallels1) Benzene and Borazine

2) Alkanes vs. Silanesa) Silanes = molecules with Si—Si bonds

i. Unstable because Si—Si (340 kJ/mol) weaker than C—C (368 kJ/mol)ii. Si less electronegative than H (1.90 vs. 2.20) so attacked by Nuiii. Si larger than C, which also makes it more easily attacked by Nuiv. Empty d-orbitals act as e-pair acceptors

b) Decomposition of Silanes

B. Parallels between Main Group and Binary Carbonyl Organometallic Species1) Electron count in relation to filled valence shells

2) Chemistry can be explained by species achieving filled valence shells

3) Group 5 Elements and 15 Electron Complexes: P vs. Ir(CO)3

4) Limitations of parallelsa) No organometallic analogue for expanded valence shell of S, P, Cl, etc…b) No analogues of IF7 or XeF4

c) Many organometallic complexes with ligands weaker than CO don’t follow the 18 electron rule, thus parallels to the main group fail

d) Loss of CO is much easier than loss of outer atoms from main group element

II. The Isolobal AnalogyA. Molecular Fragments are called “Isolobal” if the number, symmetry, energy, and shape

of the frontier orbitals and the number of electrons in them are similar1) Roald Hoffman, Nobel Prize 19822) Metal complexes can have similar reactivity/properties to main group molecules

or fragments with which they are isolobal: Methane fragments vs Oh complex

B. Molecular Fragments can be combined into molecules, even between groups1) All of the compounds below are known and stable

2) These parallels aren’t always so perfecta) H2C=CH2 is, of course, stable, but (CO)4Fe=Fe(CO)4 is not

b) Yet, both fragments form stable 3-membered rings, (but with extra CO’s)

C. Extending the Analogy1) Charged species can be included

a) Mn(CO)5 CH3 [Fe(CO)5]+ [Cr(CO)5]-

b) Coordination number should be the same2) Gain or loss of electrons from two isolobal fragments yields isolobal fragments

a) CH3 [Fe(CO)5]+ [Cr(CO)5]- (7e- or 17e- species)

b) CH3+ [Fe(CO)5]2+ [Cr(CO)5]o (6e- or 16e- species)

c) CH3- [Fe(CO)5]o [Cr(CO)5]2- (8e- or 18e- species)

3) Other ligands besides CO can be useda) Mn(CO)5 CH3 Mn(PR3)5 [Mn(Cl)5]5-

b) Cp and Benzene ligands are taken to occupy 3 sites and be 6e- donersc) Mn(CO)5 CH3 Mn(Cp)(CO)2 Mn(C6H6)(CO)2

4) Octahedral MLn fragments are isolobal with Square-Planar MLn-2 fragments

Pt2+, d8, 14e-Lobe = LUMO

Pto, d10, 14e-Lobes = non-bonding

Cro, d6, 16e-Lobe = LUMO

Feo, d8, 16e-Lobes = non-bonding

D. Applications of the Isolobal Analogy1) Seek new molecules made from isolobal fragments 2) P analogue of Cp

a) 5e- CH unit of Cp is isolobal to P atomb) Combine 5 P atoms just like 5 CH units to produce a P5 ring like Cp

3) Linear Au versions of Mn(CO)5

a) Can combine these fragments similarly with CH3, each other, etc…

III. Metal-Metal Multiple Bonds (p. 601-607)A. Parallel to Organic Bonds

1) Organic bonding: s, p orbitals give 1 , and 2 bonds

2) Metals: s, p, d orbitals give 1 , 2 , and 2

B. Discovery1) 1935 discovery of very closemetal ions, closer than in solid, pure metal (240 vs. 275 pm)

2) Cotton discovers M-M bondsin 1963 crystal structures

C. Bonding1) Quadruple bonding is routine in M-M interactions2) d-orbital interactions with other d-orbitals are most important for M-M bonding

3) Bonding in [Re2Cl8]2-

a) Re3+, d4 gives 8 d e-b) Ligand e- go into new bonding MOc) 8 d-electrons go into d) Result is BO = 4

e) bond is weak, but prevents rotationf) * distance matches visible light

[Re2Cl8]2- is blue

[Mo2Cl8]4- is red

g) Multiply bonded main groupelements are colorless (N2, CO)

because * distance is UV

h) [Os2Cl8]2- has Os3+ d5, 10 d e-

* populated, BO = 3, staggered

Cl8 group orbital interacts only with dx2-y2 group

Cl8 group orbitalsMatching dx2-y2 symmetry

1.dx2-y2 used for bonding to ligand2.This modifies the available M-M MO’sRe2Cl8

2- d4 x 2 = 8 d e-, BO = 4 ( bond, eclipsed)Os2Cl8

2- d5 x 2 = 10 d e-, BO = 3 (no bond, staggered)

4) Additional examples

5) Formal Shortness Ratio = multiple bond distance/single bond distancea) Shows the effect of multiple bonds on bond distance

6) Quintuple Bondsa) Cr-Cr and Mo-Mo complexes with quintuple (maximum) bondingb) Cr-Cr Bond length of 174.0pm and formal shortening ratio of 0.733 smallest

reported