The Two Bioinorganic Projects of Research Methodology Fall 2012

Ligand Synthesis

Complex Synthesis

Biochemical Studies

Tetraphenyl porphyrinPteridinyl

phenanthroline

DPPZ L-allox L-amino L-keto L-UN

Types of Pteridinyl Phenanthroline Ligands (and other)

Pteridinyl phenanthroline synthesis

in NaOH pH ~11

MeOH

20 h or so

Ligand Synthesis

(by Alexandra)

General Description of Ligand Synthesis

Group and Ligand Assignments for Synthesis and Characterization Group # Students ligand

complexGroup 1 — Linda Cho, Katie Guye DPPZ

[Ru(bpy)2(DPPZ)](PF6)2

Group 2 — Rachael Kahlin,Julia Heer L-allox[Ru(bpy)2(L-allox)](PF6)2

Group 3 — Julie Han,Bingqing Li L-amino[Ru(bpy)2(L-amino)](PF6)2

Group 4 — Alicia Makepeace,Misha Sims L-keto[Ru(bpy)2(L-keto)](PF6) Group 5 — Terry Huh,Maria Nam L-keto

[Ru(bpy)2(L-keto)](PF6)2

Group 6 — Anna Kalinsky,Janielle Vidal L-keto (to make L-aap)[Ru(bpy)2(L-aap)](PF6)2 Group 7— Chloe Baumann,Sara Kim L-UN (to make L-alap)[Ru(bpy)2(L-alap)](PF6)2 ‘Group’ 8 — Alexandra Kirsch L-tallox (thioalloxazine) [Ru(bpy)2(L-tallox)](PF6)2

DPPZ L-allox L-amino L-keto

L-aap L-alap

L-UN

w/ Ru w/ Ru

Group and Ligand Assignments for Synthesis and Characterization Group # Students ligand

complexGroup 1 — Linda Cho, Katie Guye DPPZ

[Ru(bpy)2(DPPZ)](PF6)2

Group 2 — Rachael Kahlin,Julia Heer L-allox[Ru(bpy)2(L-allox)](PF6)2

Group 3 — Julie Han,Bingqing Li L-amino[Ru(bpy)2(L-amino)](PF6)2

Group 4 — Alicia Makepeace,Misha Sims L-keto[Ru(bpy)2(L-keto)](PF6) Group 5 — Terry Huh,Maria Nam L-keto

[Ru(bpy)2(L-keto)](PF6)2

Group 6 — Anna Kalinsky,Janielle Vidal L-keto (to make L-aap)[Ru(bpy)2(L-aap)](PF6)2 Group 7— Chloe Baumann,Sara Kim L-UN (to make L-alap)[Ru(bpy)2(L-alap)](PF6)2 ‘Group’ 8 — Alexandra Kirsch L-tallox (thioalloxazine) [Ru(bpy)2(L-tallox)](PF6)2

DPPZ L-allox L-amino L-keto L-UN

Phenylenediamine

5,6 –diamino2,4 dihydroxy pyrimidine

4,5,6 –triamino pyrimidine

5,6 –diamino4-hydroxy pyrimidine

5,6 –diamino pyrimidine

True or false?

Blood is red because of the iron in hemoglobin.

“Red blood cells”A close-up of red bloodcells within a capillary.

Over 99 percentof the blood vessels in the

body are capillaries,even though they only hold 5 percent of the body’s blood.

Falsepor·phy·rinFunction: nounEtymology: from Greek porphyra purple

-any of various compounds with a macrocyclic structure that consists essentially of four pyrrole rings joined by four =CH- groups; especially : one (as chlorophyll or hemoglobin) containing a central metal atom and usually exhibiting biological activity

Protoporphyrin IX

Glycine +Succinyl CoA

the pyrrole ring is formed

Nature’s synthesis of Porphyrin

The Adler synthesis of simple, symmetrically substituted porphyrins:

Meso position

R = phenyl (TPP) toluyl (TTP) p-chlorophenyl (TClPP)

Ligand Synthesis: Condensations are a Theme

Schiff-Base Ligands

(Thanks, Eesha….)